Tetrahydro-1,3,5-thiadiazin-4-one derivative

ABSTRACT

A tetrahydro-1,3,5-thiadiazin-4-one represented by the general formula, ##STR1## wherein R 1 , R 2  and R 3 , which may be the same or different, represent each an alkyl group, allyl group, cycloalkyl group, alkoxyalkyl group, benzyl group, phenyl group or substituted phenyl group having as substituents alkyl groups, nitro group, halogen atoms, alkoxy groups, or trifluoromethyl group and R 2  and R 3  may also represent hydrogen atoms, is a new compound and useful for controlling insects and mites.

This invention relates to tetrahydro-1,3,5-thiadiazin-4-ones represented by the genral formula: ##STR2## wherein R¹, R² and R³, which may be the same or different, represent each an alkyl group of C₁ to C₈, allyl group, cycloalkyl group of C₃ to C₆, alkoxyalkyl group having a total of 3 to 6 carbon atoms, benzyl group, phenyl group or substituted phenyl group having as substituents one or two alkyl groups of C₁ to C₄, nitro group, halogen atoms, alkoxy groups of C₁ to C₄, or trifluoromethyl groups and R² and R³ may represent hydrogen atoms; or acid addition salts thereof. Further, this invention relates also to a process for producing the compounds represented by the above general formula or acid addition salts thereof. Furthermore, this invention relates also to insecticides and miticides containing as active ingredients the compounds represented by the above general formula or the acid addition salts thereof.

The compounds represented by the general formula (I) and the acid addition salts thereof are novel compounds.

The compounds represented by the general formula (I) may be readily synthesized by reacting carbamoyl chlorides represented by the general formula, ##STR3## wherein R¹ is the same as defined above, with thioureas represented by the general formula, ##STR4## wherein R² and R³ are the same as defined above, in the presence of a base. This reaction may be represented by the following equation and the compounds represented by the general formula (I) can be obtained in free state: ##STR5## wherein R¹, R² and R³ are as defined above.

On the other hand, a carbamoyl chloride represented by the general formula (II) and a thiourea represented by the general formula (III) can react without the addition of a base. In this case, the compound represented by the general formula (I) is obtained in the form of hydrochloride. The reaction is advantageously carried out under application of heat. Therefore, if it is desirable to obtain the compound represented by the general formula (I) in the form of hydrochloride, it is convenient to carry out the reaction in this way. When the compound represented by the general formula (I) in free state is desired, it is obtained by dissolving the hydrochloride in water and adjusting pH of the solution to neutral or slightly alkaline. The reaction may be represented by the following equation: ##STR6## wherein R¹, R² and R³ are as defined above.

Thus, the compound represented by the general formula (I) can be synthesized by either of the procedures (A) and (B). It is also possible to convert the compound represented by the general formula (I) into its salt by treating the compound with an acid of the desired type. All of these procedures are included within the scope of this invention.

The carbamoyl chloride used as one of the reactants in this invention can be synthesized, for example, by the following or similar procedures: ##STR7##

The above procedures (4) and (5) are improvement worked out by the present inventors on the procedure (2).

The procedure (1) cannot be applied to the chlorination of aniline derivatives having on their benzene nuclei substituents sensitive to chlorination. In such a case, it is necessary to follow the route of addition reaction in which a dehydration-condensation product (for example, azomethine or hexahydro-s-triazine) of an aniline derivative and formaldehyde is reacted with phosgene or trichloromethyl chloroformate, as shown in the above procedures (2) to (5). The resulting carbamoyl chloride is not necessarily isolated but the reaction mixture can be used as such in the subsequent reaction with thiourea.

The studies conducted by the present inventors revealed several interesting features of the ringforming reaction in this invention. When the substituents in the thiourea molecule are different from each other, there is a certain tendency with respect to the position occupied by the substituents R² and R³ in the ultimate compound of the formula (I). When both R² and R³ of the thiourea are alkyl groups, the substituent which occupies the position R³ in the compound (I) is generally an alkyl group having a longer carbon chain or a bulky alkyl group having a more branched carbon chain attached to the nitrogen atom, the bulkiness having preference to the chain length of the substituent. Accordingly, if a 1,3-dialkyl-thiourea having straight chain alkyl groups is used, the alkyl group with larger number of carbon atoms occupies generally the position R³ in the compound of the formula (I). If a thiourea with substituents of approximately the same bulkiness is used, there is sometimes formed a mixture of the compounds having the fomulas: ##STR8## wherein Alk¹ and Alk² represent alkyl groups having approximately the same degree of branching. In this respect, a phenylalkyl group exhibits similar tendency to the alkyl group.

In another case where the ring-forming reaction is carried out using a 1-alkyl-3-arylthiourea, the aryl group is introduced in the position R² of the compound (I). However, even when such a thiourea is used, if the alkyl group is methyl, there is obtained sometimes a mixture of the compound (I) with the methyl group at the position R² and that with the methyl group at the position R³.

Such a mixture can be separated, in some cases, into both compounds utilizing the difference in solubility.

Some typical examples wherein a mixture is obtained are shown below. ##STR9##

It is interesting that as described above, the ring-forming reaction in this invention seems to be associated with the steric structural bulkiness of R² and R³ groups.

The starting compounds represented by the formulae (II) and (III) are explained hereafter. R¹, R² and R³ are defined as previously described. The alkyl groups having 1 to 8 carbon atoms include straight chain and branched chain alkyl groups and can be shown by, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, s-butyl, n-pentyl, 3-methylbutyl, n-hexyl, heptyl, n-octyl, 1,1,3,3-tetramethylbutyl (t-octyl) and 2-ethylhexyl. The cycloalkyl groups having 3 to 6 carbon atoms include cyclohexyl, cyclopentyl, cyclopropyl and cyclobutyl. Examples of alkoxyalkyl groups having each a total of 3 to 6 carbon atoms are methoxyethyl, methoxypropyl, ethoxyethyl, propoxyethyl and butoxyethyl.

In the substituted phenyl groups represented by R¹, R² and R³, which may be the same or different, the substituent halogens are fluorine, chlorine, bromine and iodine; and the substituent alkyl or alkoxy groups of C₁ to C₄ include straight chain and branched chain groups. Typical examples of such substituted phenyl groups are chlorophenyl, dichlorophenyl, fluorophenyl, methoxyphenyl, ethoxyphenyl, isopropoxyphenyl, trifluoromethylphenyl, chlorotolyl, chloromethoxyphenyl, tolyl and dimethylphenyl groups.

The reaction in this invention is preferably carried out in a solvent which may not seriously interfere with the progress of reaction. Suitable solvents for use are water; aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone, cyclohexanone and methyl ethyl ketone; ethers such as tetrahydrofuran, dioxane and ethyl ether; halogenated hydrocarbons such as chloroform, carbon tetrachloride and chlorobenzene; alcohols such as ethanol and propanol; esters of aliphatic acids such as ethyl acetate; aliphatic amides such as dimethylformamide and dimethylacetamide; dimethyl sulfoxide and other solvents which do not severely interfere with the reaction. These solvents can also be used in combinations such as mixtures of water and organic solvents and mixtures of organic solvents.

The bases for use in the reaction include inorganic bases such as potassium hydroxide, sodium hydroxide, aqueous ammonia, potassium carbonate, sodium carbonate and sodium hydrogen carbonate; and organic bases such as triethylamine, pyridine, and 1,8-diazabicyclo-[5,4,0]-7-undecene. These bases are used, in most of the cases, in the form of aqueous solution, although they can be used in powder form, if available.

The reaction temperature can be selected from a wide range of -10° to 200° C., but the preferable temperature range is from room temperature to about 100° C. for the procedure (A) and from 60° to 130° C. for the procedure (B).

Since the reaction between a thiourea and N-chloromethyl-N-phenylcarbamoyl chloride is equimolar, the reactants are used in an equimolar ratio or in a slight excess of either reactant. The amount to be used of the base for 1 mole of either reactant is 2 moles or in slight excess for the procedure (A) and 1 mole or in slight excess for the procedure (B).

After completion of the reaction, the reaction mixture is treated with a suitable solvent to extract the compound represented by the formula (I) and the extract solution is washed, dried and freed from the solvent to obtain the compound (I) in the form of crystals or oil which, if necessary, is further purified.

When the compound represented by the formula (I) is desired to be recovered in the form of salt, either the procedure (B) is followed or the compound (I) is treated with a desired acid. The acids for use in preparing the salt are common inorganic or organic acids including HCl, HBr, H₂ SO₄, H₃ PO₄, HNO₃, HClO₄, CH₃ COOH, CCl₃ COOH, formic acid and benzenesulfonic acid.

Typical examples of the compounds represented by the formula (I) are given below.

    __________________________________________________________________________      ##STR10##                                                                     Com-                                                                           pound                                                                               Substituent group              Physical                                   No.  R.sup.1    R.sup.2    R.sup.3  property                                   __________________________________________________________________________     1    CH.sub.3   C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                         m.p. 82°-84° C.              2    CH.sub.3   i-C.sub.3 H.sub.7                                                                         i-C.sub.3 H.sub.7                                                                       m.p. 76°-77° C.              3    CH.sub.3   n-C.sub.3 H.sub.7                                                                         t-C.sub.4 H.sub.9                                                                       m.p. 81°-82° C.              4    CH.sub.3   n-C.sub.6 H.sub.13                                                                        n-C.sub.6 H.sub.13                                                                      m.p. 63°-65° C.              5    C.sub.2 H.sub.5                                                                           CH.sub.3   CH.sub.3 m.p. 43°-44° C.              6    C.sub.2 H.sub.5                                                                           CH.sub.3   t-C.sub.4 H.sub.9                                                                       m.p. 68°-69° C.              7    C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                         m.p. 68°-70° C.              8    C.sub.2 H.sub.5                                                                           i-C.sub.3 H.sub.7                                                                         i-C.sub. 3 H.sub.7                                                                      m.p. 61°-62° C.              9    CH.sub.2 CHCH.sub.2 CH.sub.3                                                              CH.sub.3   CH.sub.3 n.sub.D.sup.20 1.5615                      10   CH.sub.2 CHCH.sub.2                                                                       CH.sub.3   i-C.sub.3 H.sub.7                                                                       n.sub.D.sup.20 1.5380                      11   CH.sub.2 CHCH.sub.2                                                                       C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                         n.sub.D.sup.20 1.5397                      12   CH.sub.2 CHCH.sub.2                                                                       n-C.sub.3 H.sub.7                                                                         n-C.sub.3 H.sub.7                                                                       n.sub.D.sup.20 1.5285                      13   n-C.sub.3 H.sub.7                                                                         CH.sub.3   i-C.sub.3 H.sub.7                                                                       n.sub.D.sup.20 1.5310                      14   n-C.sub.3 H.sub.7                                                                         i-C.sub.3 H.sub.7                                                                         i-C.sub.3 H.sub.7                                                                       n.sub.D.sup.20 1.5166                      15   n-C.sub.3 H.sub.7                                                                         Benzyl     i-C.sub.3 H.sub.7                                                                       n.sub.D.sup.20 1.5185                      16   i-C.sub.3 H.sub.7                                                                         CH.sub.3   CH.sub.3 m.p. 92°-93° C.              17   i-C.sub.3 H.sub.7                                                                         CH.sub.3   C.sub.2 H.sub.5                                                                         m.p. 93°-95° C.              18   i-C.sub.3 H.sub.7                                                                         CH.sub.3   i-C.sub.3 H.sub.7                                                                       m.p. 87°-88° C.              19   i-C.sub.3 H.sub.7                                                                         CH.sub.3   Benzyl   m.p. 106°-108° C.            20   i-C.sub.3 H.sub.7                                                                         CH.sub.3   n-C.sub.6 H.sub.13                                                                      n.sub.D.sup.20 1.5199                      21   i-C.sub.3 H.sub.7                                                                         CH.sub.3   2-Ethyl- n.sub.D.sup.20 1.5180                                                 hexyl                                               22   i-C.sub.3 H.sub.7                                                                         CH.sub.3   n-C.sub.8 H.sub.17                                                                      n.sub.D.sup.20 1.5167                      23   i-C.sub.3 H.sub.7                                                                         C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                         n.sub.D.sup.20 1.5264                      24   i-C.sub.3 H.sub.7                                                                         n-C.sub.3 H.sub.7                                                                         n-C.sub.3 H.sub.7                                                                       n.sub.D.sup.20 1.5160                      25   n-C.sub.4 H.sub.9                                                                         CH.sub.3   i-C.sub.3 H.sub.7                                                                       m.p. 84°-85° C.              26   n-C.sub.4 H.sub.9                                                                         C.sub.2 H.sub.5                                                                           s-C.sub.4 H.sub.9                                                                       m.p. 81°-82° C.              27   i-C.sub.4 H.sub.9                                                                         i-C.sub.3 H.sub.7                                                                         i-C.sub.3 H.sub.7                                                                       m.p. 93°-94° C.              28   i-C.sub.3 H.sub.7                                                                         CH.sub.3   Cyclohexyl                                                                              m.p. 98°-99° C.              29   s-C.sub.4 H.sub.9                                                                         CH.sub.3   i-C.sub.3 H.sub.7                                                                       m.p. 82°-83° C.              30   s-C.sub.4 H.sub.9                                                                         C.sub.2 H.sub.5                                                                           i-C.sub.3 H.sub.7                                                                       m.p. 89°-90° C.              31   t-C.sub.4 H.sub.9                                                                         CH.sub.3   CH.sub.3 m.p. 51°-52° C.              32   t-C.sub.4 H.sub. 9                                                                        CH.sub.3   n-C.sub.3 H.sub.7                                                                       n.sub.D.sup.20 1.5273                      33   t-C.sub.4 H.sub.9                                                                         CH.sub.3   i-C.sub.3 H.sub.7                                                                       m.p. 62°-63° C.              34   t-C.sub.4 H.sub.9                                                                         CH.sub.3   n-C.sub.4 H.sub.9                                                                       n.sub.D.sup.20 1.5185                      35   t-C.sub.4 H.sub.9                                                                         CH.sub.3   s-C.sub.4 H.sub.9                                                                       m.p. 83°-84° C.              36   t-C.sub.4 H.sub.9                                                                         CH.sub.3   i-C.sub.4 H.sub.9                                                                       m.p. 77°-78° C.              37   t-C.sub.4 H.sub.9                                                                         CH.sub.3   t-C.sub.4 H.sub.9                                                                       m.p. 107°-108° C.            38   t-C.sub.4 H.sub.9                                                                         CH.sub.3   Benzyl   m.p. 125°-127° C.            39   t-C.sub.4 H.sub.9                                                                         CH.sub.3   n-C.sub.6 H.sub.13                                                                      n.sub.D.sup.20 1.5122                      40   t-C.sub.4 H.sub.9                                                                         CH.sub.3   n-C.sub.8 H.sub.17                                                                      m.p. 58°-59° C.              41   t-C.sub.4 H.sub.9                                                                         C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                         n.sub.D.sup.20 1.5235                      42   t-C.sub.4 H.sub.9                                                                         C.sub.2 H.sub.5                                                                           t-C.sub.4 H.sub.9                                                                       n.sub.D.sup.20 1.5189                      43   t-C.sub.4 H.sub.9                                                                         n-C.sub.3 H.sub.7                                                                         i-C.sub.3 H.sub.7                                                                       n.sub.D.sup.20 1.5160                      44   t-C.sub.4 H.sub.9                                                                         n-C.sub.3 H.sub.7                                                                         n-C.sub.4 H.sub.9                                                                       n.sub.D.sup.20 1.5096                      45   t-C.sub.4 H.sub.9                                                                         n-C.sub.4 H.sub.9                                                                         n-C.sub.4 H.sub.9                                                                       n.sub.D.sup.20 1.5065                      46   t-C.sub.4 H.sub.9                                                                         n-C.sub.4 H.sub.9                                                                         t-C.sub.4 H.sub.9                                                                       n.sub.D.sup.20 1.5085                      47   t-C.sub.4 H.sub.9                                                                         Benzyl     t-C.sub.4 H.sub.9                                                                       m.p. 75°-76° C.              48   t-C.sub.4 H.sub.9                                                                         i-C.sub.3 H.sub.7                                                                         t-C.sub.8 H.sub.17                                                                      m.p. 89°-91° C.              49   t-C.sub.4 H.sub.9                                                                         n-C.sub.8 H.sub.17                                                                        n-C.sub.8 H.sub.17                                                                      n.sub.D.sup.20 1.5003                      50   n-C.sub.6 H.sub.13                                                                        CH.sub.3   i-C.sub.3 H.sub.7                                                                       n.sub.D.sup.20 1.5195                      51   n-C.sub.6 H.sub.13                                                                        i-C.sub.3 H.sub.7                                                                         i-C.sub.3 H.sub.7                                                                       n.sub.D.sup.20 1.5188                      52   Cyclohexyl i-C.sub.3 H.sub.7                                                                         i-C.sub.3 H.sub.7                                                                       n.sub.D.sup.20 1.5205                      53   Cyclohexyl CH.sub.3   t-C.sub.4 H.sub.9                                                                       n.sub.D.sup.20 1.5210                      54   Benzyl     CH.sub.3   CH.sub.3 m.p. 93°-95° C.              55   Benzyl     C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                         n.sub.D.sup.20 1.5630                      56   Benzyl     n-C.sub.3 H.sub.7                                                                         n-C.sub.3 H.sub.7                                                                       n.sub.D.sup. 20 1.5653                     57   Benzyl     Benzyl     i-C.sub.3 H.sub.7                                                                       n.sub.D.sup.20 1.5780                      58   t-C.sub.8 H.sub.17                                                                        CH.sub.3   CH.sub.3 m.p. 66°-68° C.              59   t-C.sub.8 H.sub.17                                                                        CH.sub.3   i-C.sub.3 H.sub.7                                                                       n.sub.D.sup.20 1.5100                      60   t-C.sub.8 H.sub.17                                                                        CH.sub.3   CH.sub.2CHCH.sub.2                                                                      n.sub.D.sup.20 1.5210                      61   t-C.sub.8 H.sub.17                                                                        CH.sub.3   n-C.sub.4 H.sub.9                                                                       n.sub.D.sup.20 1.5112                      62   t-C.sub.8 H.sub.17                                                                        CH.sub.3   i-C.sub.4 H.sub.9                                                                       n.sub.D.sup.20 1.5110                      63   t-C.sub.8 H.sub.17                                                                        CH.sub.3   t-C.sub.4 H.sub.9                                                                       m.p. 91°-93° C.              64   n-C.sub.8 H.sub.17                                                                        CH.sub.3   CH.sub.3 n.sub.D.sup.20 1.5190                      65   n-C.sub.8 H.sub.17                                                                        CH.sub.3   i-C.sub.3 H.sub.7                                                                       n.sub.D.sup.20 1.5185                      66   i-C.sub.3 H.sub.7                                                                         Phenyl     CH.sub.3 m.p. 174°-176° C.            67   i-C.sub.3 H.sub.7                                                                         CH.sub.3                                                                                   ##STR11##                                                                              m.p. 91°-92° C.              68   i-C.sub.3 H.sub.7                                                                          ##STR12## CH.sub.3 m.p. 139° -141° C.           69   t-C.sub.4 H.sub.9                                                                         Phenyl     CH.sub.3 m.p. 125°-127° C.            70   t-C.sub.4 H.sub.9                                                                          ##STR13## CH.sub.3 m.p. 165° -166° C.           71   t-C.sub.4 H.sub.9                                                                          ##STR14## CH.sub.3 m.p. 150°-151° C.            72   t-C.sub.4 H.sub.9                                                                         CH.sub.3                                                                                   ##STR15##                                                                              m.p. 113°-115° C.            73   t-C.sub.4 H.sub.9                                                                         Phenyl     C.sub.2 H.sub.5                                                                         m.p. 117°-120° C.            74   t-C.sub.4 H.sub.9                                                                         Phenyl     n-C.sub.3 H.sub.7                                                                       m.p. 109°-110° C.            75   t-C.sub.4 H.sub.9                                                                         Phenyl     i-C.sub.3 H.sub.7                                                                       m.p. 136°-137° C.            76   t-C.sub.4 H.sub.9                                                                         Phenyl     n-C.sub.4 H.sub.9                                                                       m.p. 115°-116° C.            77   t-C.sub.4 H.sub.9                                                                         Phenyl     t-C.sub.4 H.sub.9                                                                       m.p. 133°-134° C.            78   t-C.sub.4 H.sub.9                                                                         Phenyl     Phenyl   m.p. 111°-112° C.            79   t-C.sub.4 H.sub.9                                                                         Phenyl     n-C.sub.8 H.sub.17                                                                      m.p. 59° C.                         80   t-C.sub.4 H.sub.9                                                                          ##STR16## C.sub.2 H.sub.5                                                                         m.p. 157°-158° C.            81   t-C.sub.4 H.sub.9                                                                          ##STR17## C.sub.2 H.sub.5                                                                         m.p. 103°-104° C.            82   t-C.sub.4 H.sub.9                                                                          ##STR18## CH.sub.3 m.p. 124°-125° C.            83   t-C.sub.4 H.sub.9                                                                          ##STR19## CH.sub.3 m.p. 140°-141° C.            84   t-C.sub.4 H.sub.9                                                                          ##STR20## C.sub.2 H.sub.5                                                                         m.p. 116°-117° C.            85   Benzyl     Phenyl     CH.sub.3 m.p. 109°-110° C.            86   Benzyl     Phenyl     Cyclohexyl                                                                              m.p. 101°-102° C.            87   Benzyl                                                                                     ##STR21## i-C.sub.3 H.sub.7                                                                       m.p. 1131°-132° C.           88   t-C.sub.8 H.sub.17                                                                        Phenyl     CH.sub.3 m.p. 121°-122° C.            89   t-C.sub.8 H.sub.17                                                                         ##STR22## n-C.sub.3 H.sub.7                                                                       m.p. 118°-119° C.            90   t-C.sub.8 H.sub.17                                                                         ##STR23## s-C.sub.4 H.sub.9                                                                       m.p. 93°-94° C.              91   i-C.sub.3 H.sub.7                                                                         CH.sub.3   Phenyl   NMR spectrum                                                                   (described                                                                     before)                                    92   i-C.sub.3 H.sub.7                                                                         CH.sub.3   H        n.sub.D.sup.20 1.5095                      93   t-C.sub.4 H.sub.9                                                                         CH.sub.2CHCH.sub.2                                                                        CH.sub.2CHCH.sub.2                                                                      m.p. 62°-63° C.              94   t-C.sub.4 H.sub.9                                                                         n-C.sub.3 H.sub.7                                                                         Benzyl   m.p. 45°-46° C.              95   t-C.sub.4 H.sub.9                                                                         (CH.sub.3).sub.2 CHCH.sub.2 CH.sub.2                                                      t-C.sub.4 H.sub.9                                                                       n.sub.D.sup.20 1.5477                      96   t-C.sub.4 H.sub.9                                                                         Cyclohexyl Cyclohexyl                                                                              n.sub.D.sup.20 1.5610                      97   n-C.sub.6 H.sub.13                                                                        CH.sub.3   CH.sub.3 n.sub.D.sup.20 1.5265                      98   n-C.sub.6 H.sub.13                                                                        n-C.sub.4 H.sub.9                                                                         i-C.sub.3 H.sub.7                                                                       n.sub.D.sup.20 1.5265                      99   Cyclohexyl i-C.sub.4 H.sub.9                                                                         t-C.sub.4 H.sub.9                                                                       n.sub.D.sup.20 1.5565                      100  Cyclohexyl n-C.sub.6 H.sub.13                                                                        i-C.sub.3 H.sub.7                                                                       n.sub.D.sup.20 1.5781                      101  t-C.sub.8 H.sub.17                                                                        C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                                                                         n.sub.D.sup.20 1.5116                      102                                                                                  ##STR24## CH.sub.3   i-C.sub.3 H.sub.7                                                                       n.sub.D.sup.20 1.5102                      103                                                                                  ##STR25## CH.sub.2CHCH.sub.2                                                                        i-C.sub.3 H.sub.7                                                                       n.sub.D.sup.20 1.5178                      104  s-C.sub.4 H.sub.9                                                                         Cyclopentyl                                                                               t-C.sub.4 H.sub.9                                                                       m.p. 130°-130.5° C.          105  s-C.sub.4 H.sub.9                                                                         C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2                                                        i-C.sub.3 H.sub.7                                                                       n.sub.D.sup.26 1.5019                      106  s-C.sub.4 H.sub.9                                                                          ##STR26##                                                                                 ##STR27##                                                                              m.p. 130°-131° C.            107  t-C.sub.4 H.sub.9                                                                         H          s-C.sub.4 H.sub.9                                                                       m.p. 98°-100° C.             108  t-C.sub.4 H.sub.9                                                                         C.sub.2 H.sub.5                                                                           H        m.p. 221°-222° C.            109  t-C.sub.4 H.sub.9                                                                         H          H        m.p. 123°-125° C.            110  Cyclopentyl                                                                               CH.sub.3   CH.sub.3 n.sub.D.sup.24 1.5370                      111  Cyclopentyl                                                                               i-C.sub.3 H.sub. 7                                                                        i-C.sub.3 H.sub.7                                                                       n.sub.D.sup.24 1.5156                      112  CH.sub.3 OCH.sub.2 CH.sub.2 CH.sub.2                                                      CH.sub.3   i-C.sub.3 H.sub.7                                                                       n.sub.D.sup.24 1.5043                      113  CH.sub.3 OCH.sub.2 CH.sub.2 CH.sub.2                                                      CH.sub.3   Benzyl   n.sub.D.sup.24 1.5590                      114  Cyclopentyl                                                                               Benzyl     Benzyl   m.p. 85°-86° C.              __________________________________________________________________________

    ______________________________________                                         in the case of                                                                  ##STR28##                                                                     Com-                                                                           pound                                                                          No.   R.sup.2     R.sup.3     Physical property                                ______________________________________                                         115   CH.sub.3    CH.sub.3    m.p. 68°-70° C.                    116   CH.sub.3    C.sub.2 H.sub.5                                                                            n.sub.D.sup.20 1.6034                            117   CH.sub.3    n-C.sub.3 H.sub.7                                                                          n.sub.D.sup.20 1.5902                            118   CH.sub.3    i-C.sub.3 H.sub.7                                                                          m.p. 72°-73.5° C.                  119   CH.sub.3    n-C.sub.4 H.sub.9                                                                          m.p. 30°-35° C.                    120   CH.sub.3    t-C.sub.4 H.sub.9                                                                          m.p. 87°-90° C.                    121   CH.sub.3    Benzyl      m.p. 90°-92° C.                    122   CH.sub.3    n-C.sub.8 H.sub.17                                                                         n.sub.D.sup.20 1.5551                            123   CH.sub.3    H           m.p. 101°-103° C.                  124   CH.sub.3                                                                                    ##STR29##  m.p. 113°-114° C.                  125   C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                            m.p. 55°-58° C.                    126   C.sub.2 H.sub.5                                                                            n-C.sub.3 H.sub.7                                                                          n.sub.D.sup.20 1.5800                            127   C.sub.2 H.sub.5                                                                            i-C.sub.3 H.sub.7                                                                          m.p. 69°-71° C.                    128   C.sub.2 H.sub.5                                                                            n-C.sub.4 H.sub.9                                                                          n.sub.D.sup.20 1.5709                            129   C.sub.2 H.sub.5                                                                            i-C.sub.4 H.sub.9                                                                          m.p. 85°-88° C.                    130   C.sub.2 H.sub.5                                                                            s-C.sub.4 H.sub.9                                                                          m.p. 88°-89° C.                    131   C.sub.2 H.sub.5                                                                            t-C.sub.4 H.sub.9                                                                          m.p. 93°-94° C.                    132   C.sub.2 H.sub.5                                                                            Cyclohexyl  m.p. 133°-135° C.                  133   C.sub.2 H.sub.5                                                                            n-C.sub.8 H.sub.17                                                                         n.sub.D.sup.20 1.5468                            134   n-C.sub.3 H.sub.7                                                                          n-C.sub.3 H.sub.7                                                                          n.sub.D.sup.20 1.5090                            135   n-C.sub.3 H.sub.7                                                                          i-C.sub.3 H.sub.7                                                                          n.sub.D.sup.20 1.5646                            136   n-C.sub.3 H.sub.7                                                                          s-C.sub.4 H.sub.9                                                                          n.sub.D.sup.20 1.5579                            137   n-C.sub.3 H.sub.7                                                                          t-C.sub.4 H.sub.9                                                                          m.p. 65°-67° C.                    138   n-C.sub.3 H.sub.7                                                                          Cyclohexyl  n.sub.D.sup. 20 1.5697                           139   CH.sub.2CHCH.sub.2                                                                         CH.sub.2CHCH.sub.2                                                                         n.sub.D.sup.20 1.5941                            140   CH.sub.2CHCH.sub.2                                                                         n-C.sub.3 H.sub.7                                                                          n.sub.D.sup.26 1.5753                            141   CH.sub.2CHCH.sub.2                                                                         i-C.sub.3 H.sub.7                                                                          n.sub.D.sup.26 1.5722                            142   CH.sub.2CHCH.sub.2                                                                         s-C.sub.4 H.sub.9                                                                          n.sub.D.sup.26 1.5719                            143   CH.sub.2CHCH.sub.2                                                                         t-C.sub.4 H.sub.9                                                                          m.p. 46°-47° C.                    144   i-C.sub.3 H.sub.7                                                                          i-C.sub.3 H.sub.7                                                                          m.p. 92°-94° C.                    145   i-C.sub.3 H.sub.7                                                                          t-C.sub.4 H.sub.9                                                                          m.p. 104°-106° C.                  146   n-C.sub.4 H.sub.9                                                                          n-C.sub.4 H.sub.9                                                                          n.sub.D.sup.20 1.5604                            147   n-C.sub.4 H.sub.9                                                                          i-C.sub.3 H.sub.7                                                                          n.sub.D.sup.20 1.5580                            148   i-C.sub.4 H.sub.9                                                                          i-C.sub.4 H.sub.9                                                                          m.p. 82°-83° C.                    149   i-C.sub.4 H.sub.9                                                                          i-C.sub.3 H.sub.7                                                                          m.p. 80°-82° C.                    150   i-C.sub.4 H.sub.9                                                                          t-C.sub.4 H.sub.9                                                                          m.p. 75°-77° C.                    151   s-C.sub.4 H.sub.9                                                                          s-C.sub.4 H.sub.9                                                                          n.sub.D.sup.20 1.5561                            152   s-C.sub.4 H.sub.9                                                                          t-C.sub.4 H.sub.9                                                                          n.sub.D.sup.20 1.5544                            153   n-C.sub.6 H.sub.13                                                                         i-C.sub.3 H.sub.7                                                                          n.sub.D.sup.26 1.5464                            154   n-C.sub.6 H.sub.13                                                                         n-C.sub.6 H.sub.13                                                                         n.sub.D.sup.20 1.5420                            155   Cyclohexyl  t-C.sub.4 H.sub.9                                                                          m.p. 86°-89° C.                    156   i-C.sub.3 H.sub.7                                                                          t-C.sub.8 H.sub.17                                                                         n.sub.D.sup.25 1.5382                            157   s-C.sub.4 H.sub.9                                                                          t-C.sub.8 H.sub.17                                                                         n.sub.D.sup.20 1.5461                            158   Benzyl      i-C.sub.3 H.sub.7                                                                          m.p. 124°-125° C.                  159   Benzyl      t-C.sub.4 H.sub.9                                                                          n.sub.D.sup.26 1.5910                            160   n-C.sub.8 H.sub.17                                                                         i-C.sub.3 H.sub.7                                                                          n.sub.D.sup.20 1.5400                            161   n-C.sub.8 H.sub.17                                                                         s-C.sub.4 H.sub.9                                                                          n.sub.D.sup.20 1.5351                            162   Phenyl      C.sub.2 H.sub.5                                                                            m.p. 113°-115° C.                  163   Phenyl      s-C.sub.4 H.sub.9                                                                          m.p. 134°-135.5° C.                164                                                                                   ##STR30##  i-C.sub.3 H.sub.7                                                                          m.p. 175°-177° C.                  165                                                                                   ##STR31##  C.sub.2 H.sub.5                                                                            m.p. 116°-117° C.                  166                                                                                   ##STR32##  CH.sub.3    m.p. 121°-123° C.                  167                                                                                   ##STR33##  i-C.sub.3 H.sub.7                                                                          m.p. 182°-184° C.                  168                                                                                   ##STR34##  s-C.sub.4 H.sub.9                                                                          n.sub.D.sup.20 1.5538                            169   Phenyl      Phenyl      m.p. 193°-194° C.                  170                                                                                   ##STR35##  C.sub.2 H.sub.5                                                                            m.p. 136°-137° C.                  171                                                                                   ##STR36##  CH.sub.3    m.p. 111°-112° C.                  172                                                                                   ##STR37##  n-C.sub.3 H.sub.7                                                                          m.p. 146°-147° C.                  173   s-C.sub.4 H.sub.9                                                                          i-C.sub.3 H.sub.7                                                                          NMR                                                                            spectrum                                         174   i-C.sub.3 H.sub.7                                                                          s-C.sub.4 H.sub.9                                                                          NMR        des-                                                                spectrum   cribed                                175   CH.sub.3    Phenyl      NMR        be-                                                                 spectrum   fore                                  176   Phenyl      CH.sub.3    NMR                                                                            spectrum                                         177   CH.sub.3                                                                                    ##STR38##  Obtained as a mixture with compound   No.                                      166                                              178   H           H           m.p. 176° C.                                                            (decomp.)                                        179   CH.sub.3 OCH.sub.2 CH.sub.2                                                                i-C.sub.3 H.sub.7                                                                          n.sub.D.sup.20 1.5640                            180   CH.sub.3 OCH.sub.2 CH.sub.2                                                                t-C.sub.4 H.sub.9                                                                          n.sub.D.sup.20 1.5559                            181   C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2                                                         i-C.sub.3 H.sub.7                                                                          n.sub.D.sup.20 1.5572                            182   C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2                                                         t-C.sub.4 H.sub.9                                                                          m.p. 74°-75.5° C.                  183   Cyclopentyl t-C.sub.4 H.sub.9                                                                          m.p. 103°-104° C.                  184   t-C.sub.4 H.sub.9                                                                          t-C.sub.4 H.sub.9                                                                          m.p. 109°-115° C.                  185                                                                                   ##STR39##                                                                                  ##STR40##  m.p. 172°-175° C.                  ______________________________________                                    

    __________________________________________________________________________      ##STR41##                                                                     Com-                                                                           pound                        Physical                                          No. X    R.sup.2   R.sup.3   property                                          __________________________________________________________________________     186 4-Cl H         i-C.sub.3 H.sub.7                                                                        m.p. 190°-197° C.                                                (decomp.)                                         187 4-Cl H         t-C.sub.4 H.sub.9                                                                        m.p. 210°-214° C.                                                (decomp.)                                         188 4-Cl CH.sub.3  CH.sub.3  m.p. 98°-100° C.                    189 4-Cl CH.sub.3  i-C.sub.3 H.sub.7                                                                        m.p. 106°-108° C.                   190 4-Cl C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                          m.p. 123°-125° C.                   191 4-Cl C.sub.2 H.sub.5                                                                          t-C.sub.4 H.sub.9                                                                        m.p. 154°-157° C.                   192 4-Cl n-C.sub.3 H.sub.7                                                                        n-C.sub.3 H.sub.7                                                                        m.p. 81°-82° C.                     193 4-Cl n-C.sub.3 H.sub.7                                                                        i-C.sub.3 H.sub.7                                                                        m.p. 61°-63° C.                     194 4-Cl i-C.sub. 3 H.sub.7                                                                       i-C.sub.3 H.sub.7                                                                        m.p. 127°-129° C.                   195 4-Cl n-C.sub.3 H.sub.7                                                                        t-C.sub.4 H.sub.9                                                                        m.p. 68°-69° C.                     196 4-Cl i-C.sub.3 H.sub.7                                                                        t-C.sub.4 H.sub.9                                                                        m.p. 123°-125° C.                   197 4-Cl s-C.sub.4 H.sub.9                                                                        s-C.sub.4 H.sub.9                                                                        m.p. 102°-103° C.                   198 4-Cl s-C.sub.4 H.sub.9                                                                        t-C.sub.4 H.sub.9                                                                        m.p. 99°-100° C.                    199 4-Cl CH.sub.2CHCH.sub.2                                                                       CH.sub.2CHCH.sub.2                                                                       n.sub.D.sup.30 1.6003                             200 4-Cl CH.sub.2CHCH.sub.2                                                                       i-C.sub.3 H.sub.7                                                                        n.sub.D.sup.30 1.5833                             201 4-Cl CH.sub.3                                                                                  ##STR42##                                                                               n.sub.D.sup.28 1.6293                             202 4-Cl CH.sub.2CHCH.sub.2                                                                        ##STR43##                                                                               n.sub.D.sup.28 1.6221                             203 4-Cl                                                                                 ##STR44##                                                                               i-C.sub.3 H.sub.7                                                                        n.sub.D.sup.28 1.5978                             204 4-Cl                                                                                 ##STR45##                                                                               t-C.sub.4 H.sub.9                                                                        m.p. 87°-89° C.                     205 4-Cl                                                                                 ##STR46##                                                                               i-C.sub.3 H.sub.7                                                                        m.p. 153°- 155° C.                  206 4-Cl i-C.sub.3 H.sub.7                                                                        t-C.sub.8 H.sub.17                                                                       m.p. 124°-125° C.                   207 4-Cl CH.sub.3 OC.sub.2 H.sub.4                                                                i-C.sub.3 H.sub.7                                                                        n.sub.D.sup.20 1.5728                             208 4-Cl                                                                                 ##STR47##                                                                               t-C.sub.4 H.sub.9                                                                        m.p. 147°-148° C.                   209 4-Cl                                                                                 ##STR48##                                                                               CH.sub.3  m.p. 187°-188° C.                   210 4-Cl                                                                                 ##STR49##                                                                               CH.sub.3  m.p. 148°-149° C.                   211 4-Cl                                                                                 ##STR50##                                                                               C.sub.2 H.sub.5                                                                          m.p. 149°-150° C.                   212 4-Cl CH.sub.3  n-C.sub.6 H.sub.13                                                                       m.p. 75°-76° C.                     213 3-Cl CH.sub.3  CH.sub.3  m.p. 111°-112° C.                                                (HCl salt: m.p.                                                                180°-183° C. decomp.)               214 3-Cl CH.sub.3  i-C.sub.3 H.sub.7                                                                        m.p. 108°-111° C.                   215 3-Cl C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                          m.p. 106°-108° C.                                                (HCl salt: m.p.                                                                199°-200° C.)                       216 3-Cl C.sub.2 H.sub.5                                                                          t-C.sub.4 H.sub.9                                                                        m.p. 62°-63° C.                     217 3-Cl CH.sub.2 CHCH.sub.2                                                                      i-C.sub.3 H.sub.7                                                                        n.sub.D.sup.19 1.5857                                                          (HCl salt: m.p.                                                                179° C. decomp.)                           218 3-Cl CH.sub.2 CHCH.sub.2                                                                      t-C.sub.4 H.sub.9                                                                        n.sub.D.sup.19 1.5796                             219 3-Cl CH.sub.2 CHCH.sub.2                                                                       ##STR51##                                                                               n.sub.D.sup.19 1.6107                             220 3-Cl i-C.sub.3 H.sub.7                                                                        i-C.sub.3 H.sub.7                                                                        m.p. 81°-82° C.                     221 3-Cl i-C.sub.3 H.sub.7                                                                        t-C.sub.4 H.sub.9                                                                        m.p. 113°-115° C.                                                (HCl salt: m.p.                                                                152° C. decomp.)                           222 3-Cl i-C.sub.3 H.sub.7                                                                        t-C.sub.8 H.sub.17                                                                       n.sub.D.sup.19 1.5406                             223 3-Cl i-C.sub.4 H.sub.9                                                                        t-C.sub.4 H.sub.9                                                                        n.sub.D.sup.20 1.5542                             224 3-Cl s-C.sub.4 H.sub.9                                                                        s-C.sub.4 H.sub.9                                                                        n.sub.D.sup.20 1.5652                             225 3-Cl s-C.sub.4 H.sub.9                                                                        t-C.sub.4 H.sub.9                                                                        m.p. 75°-76° C.                                                  (HCl salt: m.p.                                                                186° C. decomp.)                           226 3-Cl                                                                                 ##STR52##                                                                               CH.sub.3  m.p. 185°-186° C.                   227 3-Cl                                                                                 ##STR53##                                                                               CH.sub.3  m.p. 148°-149° C.                   228 3-Cl CH.sub.3 OC.sub.4 H.sub.9                                                                i-C.sub.3 H.sub.7                                                                        n.sub.D.sup.20 1.5731                             229 3-Cl CH.sub.3 OC.sub.2 H.sub.4                                                                t-C.sub.4 H.sub.9                                                                        n.sub.D.sup.20 1.5711                             230 3-Cl i-C.sub.3 H.sub.7                                                                         ##STR54##                                                                               m.p. 105°-106° C.                   231 3-Cl                                                                                 ##STR55##                                                                                ##STR56##                                                                               m.p. 158°-159° C.                   232 3-Cl n-C.sub.3 H.sub.7                                                                        t-C.sub.4 H.sub.9                                                                        n.sub.D.sup.22 1.5740                             233 3-Cl                                                                                 ##STR57##                                                                               i-C.sub.3 H.sub.7                                                                        n.sub.D.sup.20 1.5750                             234 3-Cl n-C.sub.6 H.sub.13                                                                       i-C.sub.3 H.sub.7                                                                        n.sub.D.sup.20 1.5635                             235 3-Cl                                                                                 ##STR58##                                                                               s-C.sub.4 H.sub.9                                                                        n.sub.D.sup.20 1.5518                             236 3-Cl n-C.sub.4 H.sub. 9                                                                       t-C.sub.4 H.sub.9                                                                        n.sub.D.sup.23 1.5600                             237 3-Cl                                                                                 ##STR59##                                                                               i-C.sub.3 H.sub.7                                                                        m.p. 158°-159° C.                   238 2-Cl CH.sub.3  CH.sub.3  m.p. 142°-144° C.                                                (HCl salt: m.p.                                                                198°-200° C. decomp.)               239 2-Cl C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                          m.p. 90°-92° C.                                                  (HCl salt: m.p.                                                                167°-170° C.                                                     decomp.)                                          240 2-Cl CH.sub.3  i-C.sub.3 H.sub.7                                                                        n.sub.D.sup.22 1.5725                             241 2-Cl C.sub.2 H.sub.5                                                                          t-C.sub.4 H.sub.9                                                                        m.p. 94°-96° C.                     242 2-Cl CH.sub.2CHCH.sub.2                                                                       i-C.sub.3 H.sub.7                                                                        n.sub.D.sup.13 1.5831                             243 2-Cl CH.sub.2CHCH.sub.2                                                                       t-C.sub.4 H.sub.9                                                                        m.p. 105°-107° C.                   244 2-Cl i-C.sub.3 H.sub.7                                                                        i-C.sub.3 H.sub.7                                                                        m.p. 95°-96° C.                     245 2-Cl i-C.sub.3 H.sub.7                                                                        t-C.sub.4 H.sub.9                                                                        m.p. 88°-89° C.                                                  (HCl salt: m.p.                                                                201° C. decomp.)                           246 2-Cl i-C.sub.3 H.sub.7                                                                        n-C.sub.6 H.sub.13                                                                       n.sub.D.sup.13 1.5581                             247 2-Cl i-C.sub.3 H.sub.7                                                                        t-C.sub.8 H.sub.17                                                                       n.sub.D.sup.13 1.5822                             248 2-Cl s-C.sub.4 H.sub.9                                                                        s-C.sub.4 H.sub.9                                                                        m.p. 89°-90° C.                     249 2-Cl s-C.sub.4 H.sub.9                                                                        t-C.sub.4 H.sub.9                                                                        m.p. 67°-68° C.                     250 2-Cl                                                                                 ##STR60##                                                                               i-C.sub.3 H.sub.7                                                                        m.p. 95°-97° C.                     251 2-Cl                                                                                 ##STR61##                                                                                ##STR62##                                                                               (HCl salt: m.p. 127°-130° C.                                     decomp.)                                          252 2-Cl i-C.sub.3 H.sub.7                                                                         ##STR63##                                                                               m.p. 123°-125° C.                   253 2-Cl i-C.sub.4 H.sub.9                                                                        s-C.sub.4 H.sub.9                                                                        n.sub.D.sup.21 1.5582                             254 2-Cl n-C.sub.6 H.sub.13                                                                       i-C.sub.3 H.sub.7                                                                        n.sub.D.sup.13 1.5581                             255 2-Cl                                                                                 ##STR64##                                                                               i-C.sub.3 H.sub.7                                                                        m.p. 75°-77° C.                     256 2-Cl                                                                                 ##STR65##                                                                               C.sub.2 H.sub. 5                                                                         m.p. 77°-79° C.                     257 2-Cl                                                                                 ##STR66##                                                                               CH.sub.3  m.p. 167°-168° C.                   258 2-Cl CH.sub.3 OCH.sub.2 CH.sub.2 CH.sub.2                                                     t-C.sub.4 H.sub.9                                                                        m.p. 87°-88° C.                     259 3-CF.sub.3                                                                          CH.sub.3  i-C.sub.3 H.sub.7                                                                        n.sub.D.sup.30 1.5264                             260 3-CF.sub.3                                                                          C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                          n.sub.D.sup.30 1.5268                             261 3-CF.sub.3                                                                          C.sub.2 H.sub.5                                                                          t-C.sub.4 H.sub.9                                                                        n.sub.D.sup.30 1.5165                             262 3-CF.sub.3                                                                          CH.sub.2CHCH.sub.2                                                                       i-C.sub.3 H.sub.7                                                                        n.sub.D.sup.24 1.5357                             263 3-CF.sub.3                                                                          n-C.sub.3 H.sub.7                                                                        n-C.sub.3 H.sub.7                                                                        n.sub.D.sup.30 1.5233                             264 3-CF.sub.3                                                                          n-C.sub.3 H.sub.7                                                                        i-C.sub.3 H.sub.7                                                                        n.sub.D.sup.24 1.5262                             265 3-CF.sub.3                                                                          i-C.sub.3 H.sub.7                                                                        i-C.sub.3 H.sub.7                                                                        m.p. 67°-68° C.                     266 3-CF.sub.3                                                                          i-C.sub.3 H.sub.7                                                                        t-C.sub.8 H.sub.17                                                                       n.sub.D.sup.24 1.5089                             267 3-CF.sub.3                                                                          CH.sub.2CHCH.sub.2                                                                       s-C.sub.4 H.sub.9                                                                        n.sub.D.sup.24 1.5392                             268 3-CF.sub.3                                                                          CH.sub.2CHCH.sub.2                                                                       t-C.sub.4 H.sub.9                                                                        n.sub.D.sup.24 1.5262                             269 3-CF.sub.3                                                                          i-C.sub.3 H.sub.7                                                                        s-C.sub.4 H.sub.9                                                                        n.sub.D.sup.24 1.5219                             270 3-CF.sub.3                                                                          i-C.sub.3 H.sub.9                                                                        t-C.sub.3 H.sub.7                                                                        m.p. 52°-53° C.                                                  (HCl salt: m.p.                                                                160°-164° C.)                       271 3-CF.sub.3                                                                          i-C.sub.4 H.sub.9                                                                        s-C.sub.4 H.sub.9                                                                        n.sub.D.sup.24 1.5140                             272 3-CF.sub.3                                                                          s-C.sub.4 H.sub.9                                                                        s-C.sub.4 H.sub.9                                                                        n.sub.D.sup.24 1.5238                             273 3-CF.sub.3                                                                          i-C.sub.4 H.sub.9                                                                        t-C.sub.4 H.sub.9                                                                        n.sub.D.sup.24 1.5130                             274 3-CF.sub.3                                                                          s-C.sub.4 H.sub.9                                                                        t-C.sub.4 H.sub.9                                                                        (HCl salt: m.p.                                                                186.4° C. decomp.)                         275 4-F  H         i-C.sub.3 H.sub.7                                                                        m.p. 188°-190° C.                   276 4-F  H         t-C.sub.4 H.sub.9                                                                        m.p. 205°-212° C.                                                decomp.                                           277 4-F  CH.sub.3  CH.sub.3  m.p. 105°-106° C.                                                (HCl salt: m.p.                                                                221° C. decomp.)                           278 4-F  C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                          m.p. 99°-100° C.                                                 (HCl salt: m.p.                                                                185° C. decomp.)                           279 4-F  CH.sub.3  i-C.sub.3 H.sub.7                                                                        m.p. 119°-120° C.                                                (HCl salt: m.p.                                                                202° C. decomp.)                           280 4-F  C.sub.2 H.sub.5                                                                          t-C.sub.4 H.sub.9                                                                        m.p. 99°-100° C.                    281 4-F  n-C.sub.3 H.sub.7                                                                        n-C.sub.6 H.sub.13                                                                       n.sub.D.sup.20 1.5596                             282 4-F  i-C.sub.3 H.sub.7                                                                        t-C.sub.4 H.sub.9                                                                        m.p. 109°-110° C.                   283 4-F  s-C.sub.4 H.sub.9                                                                        s-C.sub.4 H.sub.9                                                                        m.p. 55°-56° C.                     284 4-F  s-C.sub.4 H.sub.9                                                                        t-C.sub.4 H.sub.9                                                                        m.p. 61°-62° C.                     285 4-F  i-C.sub.3 H.sub.7                                                                        i-C.sub.3 H.sub.7                                                                        m.p. 119°-120° C.                   286 4-F                                                                                  ##STR67##                                                                               i-C.sub.3 H.sub.7                                                                        m.p. 141°-142° C.                   287 4-F  C.sub.2 H.sub.5                                                                          H         m.p. 88°-91° C.                     288 4-F                                                                                  ##STR68##                                                                               t-C.sub.4 H.sub.9                                                                        m.p. 103°-104° C.                   289 4-F  CH.sub.3  CH.sub.2 CHCH.sub.2                                                                      m.p. 81°-82° C.                     290 4-F                                                                                  ##STR69##                                                                               C.sub.2 H.sub.5                                                                          m.p. 162°-163° C.                   291 4-Br CH.sub.3  CH.sub.3  m.p. 136°-137° C.                   292 4-Br C.sub.2 H.sub.5                                                                          t-C.sub.4 H.sub.9                                                                        m.p. 131°-132° C.                   293 4-Br i-C.sub.3 H.sub.7                                                                        i-C.sub.3 H.sub.7                                                                        m.p. 121°-122° C.                   294 4-Br i-C.sub.3 H.sub.7                                                                        t-C.sub.4 H.sub.9                                                                        m.p. 117°-118° C.                   295 4-Br s-C.sub.4 H.sub.9                                                                        t-C.sub.4 H.sub.9                                                                        m.p. 68°-69° C.                     296 2-CH.sub.3                                                                          CH.sub.3  CH.sub.3  m.p. 116°-117° C.                   297 2-CH.sub.3                                                                          CH.sub.3  i-C.sub.3 H.sub.7                                                                        n.sub.D.sup.20 1. 5703                            298 2-CH.sub.3                                                                          C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                          m.p. 75°-76° C.                     299 2-CH.sub.3                                                                          C.sub.2 H.sub.5                                                                          t-C.sub.4 H.sub.9                                                                        m.p. 92° C.                                300 2-CH.sub.3                                                                          CH.sub.2CHCH.sub.2                                                                       t-C.sub.4 H.sub.9                                                                        m.p. 90.8° C.                              301 2-CH.sub.3                                                                          i-C.sub.3 H.sub.7                                                                        i-C.sub.3 H.sub.7                                                                        n.sub.D.sup.20 1.5587                             302 2-CH.sub.3                                                                          i-C.sub.3 H.sub.7                                                                        t-C.sub. 4 H.sub.9                                                                       m.p. 97.5°-99° C.                   303 2-CH.sub.3                                                                          s-C.sub.4 H.sub.9                                                                        t-C.sub.4 H.sub.9                                                                        n.sub.D.sup.20 1.5483                             304 2-CH.sub.3                                                                          n-C.sub.6 H.sub.13                                                                       i-C.sub.3 H.sub.7                                                                        n.sub.D.sup.20 1.5421                             305 2-CH.sub.3                                                                          i-C.sub.3 H.sub.7                                                                         ##STR70##                                                                               m.p. 87° C.                                306 2-CH.sub.3                                                                           ##STR71##                                                                               i-C.sub.3 H.sub.7                                                                        m.p. 91.1° C.                              307 2-CH.sub.3                                                                           ##STR72##                                                                                ##STR73##                                                                               n.sub.D.sup.20 1.5568                             308 2-CH.sub.3                                                                           ##STR74##                                                                                ##STR75##                                                                               n.sub.D.sup.20 1.5568                             309 4-CH.sub.3                                                                          CH.sub.3  CH.sub.3  m.p. 80°-81° C.                     310 4-CH.sub.3                                                                          CH.sub.3  i-C.sub.3 H.sub.7                                                                        m.p. 90°-91° C.                     311 4-CH.sub.3                                                                          CH.sub.3  t-C.sub.4 H.sub.9                                                                        m.p. 102°-105° C.                   312 4-CH.sub.3                                                                          C.sub.2 H.sub.5                                                                          t-C.sub.4 H.sub.9                                                                        m.p. 83°-85° C.                     313 4-CH.sub.3                                                                          n-C.sub.3 H.sub.7                                                                        n-C.sub.3 H.sub.7                                                                        m.p. 62°-64°  C.                    314 4-CH.sub.3                                                                          n-C.sub.3 H.sub.7                                                                        i-C.sub.3 H.sub.7                                                                        m.p. 89°-90° C.                     315 4-CH.sub.3                                                                          CH.sub.2CHCH.sub.2                                                                       i-C.sub.3 H.sub.7                                                                        n.sub.D.sup.20 1.5722                             316 4-CH.sub.3                                                                          i-C.sub.3 H.sub.7                                                                        i-C.sub.3 H.sub.7                                                                        m.p. 118°-119° C.                   317 4-CH.sub.3                                                                          n-C.sub.3 H.sub.7                                                                        t-C.sub.4 H.sub.9                                                                        m.p. 89°-90° C.                     318 4-CH.sub.3                                                                          i-C.sub.3 H.sub.7                                                                        t-C.sub.4 H.sub.9                                                                        m.p. 118°-120° C.                   319 4-CH.sub.3                                                                          s-C.sub.4 H.sub.9                                                                        t-C.sub.4 H.sub.9                                                                        m.p.85°-87° C.                      320 4-CH.sub.3                                                                           ##STR76##                                                                               i-C.sub.3 H.sub.7                                                                        m.p. 100°-101° C.                   321 4-CH.sub.3                                                                           ##STR77##                                                                                ##STR78##                                                                               m.p. 152°-153° C.                   322 4-CH.sub.3                                                                           ##STR79##                                                                               i-C.sub.3 H.sub.7                                                                        m.p. 201°-203° C.                   323 4-CH.sub.3                                                                           ##STR80##                                                                               t-C.sub.4 H.sub.9                                                                        m.p. 158°-160 ° C.                  324 3-CH.sub.3                                                                          C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                          n.sub. D.sup.20 1.5814                            325 3-CH.sub.3                                                                          i-C.sub.3 H.sub.7                                                                        i-C.sub.3 H.sub.7                                                                        m.p. 71.0° C.                              326 3-CH.sub.3                                                                          i-C.sub.3 H.sub.7                                                                        t-C.sub.4 H.sub.9                                                                        m.p. 104.3° C.                             327 3-CH.sub.3                                                                          s-C.sub.4 H.sub.9                                                                        s-C.sub.4 H.sub.9                                                                        n.sub.D.sup.20 1.5528                             328 3-CH.sub.3                                                                          s-C.sub.4 H.sub.9                                                                        t-C.sub.4 H.sub.9                                                                        n.sub.D.sup.20 1.5546                             329 3-CH.sub.3                                                                           ##STR81##                                                                               i-C.sub.3 H.sub.7                                                                        m.p. 82°-84° C.                     330 3-CH.sub.3                                                                          n-C.sub.6 H.sub.13                                                                       i-C.sub.3 H.sub.7                                                                        n.sub.D.sup.20 1.5465                             331 4-C.sub.2 H.sub.5                                                                   CH.sub.3  CH.sub.3  n.sub.D.sup.20 1.5922                             332 4-C.sub.2 H.sub.5                                                                   i-C.sub.3 H.sub.7                                                                        i-C.sub.3 H.sub.7                                                                        m.p. 81°-82.5° C.                   333 4-C.sub.2 H.sub.5                                                                   i-C.sub.3 H.sub.7                                                                        t-C.sub.4 H.sub.9                                                                        m.p. 70°-72° C.                     334 4-C.sub.2 H.sub.5                                                                   s-C.sub.4 H.sub.9                                                                        t-C.sub.4 H.sub.9                                                                        m.p. 67.5° C.                              335 2-C.sub.2 H.sub.5                                                                   CH.sub.3  CH.sub.3  m.p. 122.0° C.                             336 2-C.sub.2 H.sub.5                                                                   CH.sub.2CHCH.sub.2                                                                       i-C.sub.3 H.sub.7                                                                        n.sub.D.sup. 20 1.5601                            337 2-C.sub.2 H.sub.5                                                                   i-C.sub.3 H.sub.7                                                                        i-C.sub.3 H.sub.7                                                                        n.sub.D.sup.20 1.5510                             338 2-C.sub.2 H.sub.5                                                                   i-C.sub.3 H.sub.7                                                                        t-C.sub.4 H.sub.9                                                                        n.sub.D.sup.20 1.5463                             339 2-C.sub.2 H.sub.5                                                                   s-C.sub.4 H.sub.9                                                                        t-C.sub.4 H.sub.9                                                                        n.sub.D.sup.20 1.5401                             340 2-C.sub.3 H.sub.7 -i                                                                CH.sub.3  CH.sub.3  m.p. 101°-102° C.                   341 2-C.sub.3 H.sub.7 -i                                                                C.sub.2 H.sub.5                                                                          t-C.sub.4 H.sub.9                                                                        m.p. 84°-85° C.                     342 2-C.sub.3 H.sub.7 -i                                                                i-C.sub.3 H.sub.7                                                                        i-C.sub.3 H.sub.7                                                                        m.p. 85°-86° C.                     343 2-C.sub.3 H.sub.7 -i                                                                i-C.sub.3 H.sub.7                                                                        t-C.sub.4 H.sub.9                                                                        m.p. 108°-109° C.                   344 2-C.sub.3 H.sub.7 -i                                                                s-C.sub.4 H.sub.9                                                                        t-C.sub.4 H.sub.9                                                                        m.p. 74°-76° C.                     345 2-C.sub.3 H.sub.7 -i                                                                CH.sub.2CHCH.sub.2                                                                       CH.sub.2CHCH.sub.2                                                                       m.p. 93°-95° C.                     346 2-C.sub.3 H.sub.7 -i                                                                CH.sub.2CHCH.sub.2                                                                       i-C.sub.3 H.sub.7                                                                        n.sub.D.sup.20 1.5526                             347 4-CH.sub.3 O                                                                        CH.sub.3  i-C.sub.3 H.sub. 7                                                                       m.p. 69.5° C.                              348 4-CH.sub.3 O                                                                        C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                          m.p. 100° C.                               349 4-CH.sub.3 O                                                                        C.sub.2 H.sub.5                                                                          t-C.sub.4 H.sub.9                                                                        n.sub.D .sup.20 1.5591                            350 4-CH.sub.3 O                                                                        CH.sub.2CHCH.sub.2                                                                       i-C.sub.3 H.sub.7                                                                        m.p. 80.1° C.                              351 4-CH.sub.3 O                                                                        n-C.sub.3 H.sub.7                                                                        i-C.sub.3 H.sub.7                                                                        m.p. 96°-97° C.                     352 4-CH.sub.3 O                                                                        i-C.sub.3 H.sub.7                                                                        i-C.sub.3 H.sub.7                                                                        m.p. 67°-68° C.                     353 4-CH.sub.3 O                                                                        i-C.sub.3 H.sub.7                                                                        t-C.sub.4 H.sub.9                                                                        m.p. 99°-101.5° C.                  354 4-CH.sub.3 O                                                                        n-C.sub.3 H.sub.7                                                                         ##STR82##                                                                               m.p. 85.5° C.                              355 4-CH.sub.3 O                                                                        s-C.sub.4 H.sub.9                                                                        t-C.sub.4 H.sub.9                                                                        m.p. 63° C.                                356 4-CH.sub.3 0                                                                         ##STR83##                                                                               i-C.sub.3 H.sub.7                                                                        m.p. 114° C.                               357 4-CH.sub.3 O                                                                        n-C.sub.8 H.sub.17                                                                       s-C.sub.4 H.sub.9                                                                        n.sub.D.sup.20 1.5296                             358 4-CH.sub.3 O                                                                         ##STR84##                                                                               t-C.sub.4 H.sub.9                                                                        m.p. 167°-168° C.                   359 4-CH.sub.3 O                                                                         ##STR85##                                                                               i-C.sub.3 H.sub.7                                                                        m.p. 159.1° C.                             360 2-CH.sub.3 O                                                                        i-C.sub.3 H.sub.7                                                                        t-C.sub.4 H.sub.9                                                                        m.p. 88.7° C.                              361 4-F  s-C.sub.4 H.sub.9                                                                        i-C.sub.3 H.sub.7                                                                        NMR spectrum                                                                   given herein-                                                                  after                                             362 4-F  i-C.sub.3 H.sub.7                                                                        s-C.sub.4 H.sub.9                                                                        NMR spectrum                                                                   given herein-                                                                  after                                             __________________________________________________________________________

    __________________________________________________________________________      ##STR86##                                                                     Compound                                                                       No.    Y   Z     R.sup.2                                                                                R.sup.3                                                                               Physical property                              __________________________________________________________________________     363   H   4-NO.sub.2                                                                           i-C.sub.3 H.sub.7                                                                      H       m.p. 160°-163° C.                364   H   4-NO.sub.2                                                                           i-C.sub.3 H.sub.7                                                                      t-C.sub.4 H.sub.9                                                                      m.p. 130°-131° C.                365   H   4-OH  i-C.sub.3 H.sub.7                                                                      t-C.sub.4 H.sub.9                                                                      m.p. 197°-198° C.                366   2-NO.sub.2                                                                         4-NO.sub.2                                                                           i-C.sub.3 H.sub.7                                                                      i-C.sub.3 H.sub.7                                                                      m.p. 130°-133° C.                367   H   4-C.sub.2 H.sub.5 O                                                                  i-C.sub.3 H.sub.7                                                                      t-C.sub.4 H.sub.9                                                                      m.p. 79°-80° C.                  368   H   4-C.sub.2 H.sub.5 O                                                                  s-C.sub.4 H.sub.9                                                                      t-C.sub.4 H.sub.9                                                                      m.p. 66°-67° C.                  369   H   4-C.sub.2 H.sub.5 O                                                                  n-C.sub.6 H.sub.13                                                                     i-C.sub.3 H.sub.7                                                                      m.p. 78°-79° C.                  370   H   4-i-C.sub.3 H.sub.7 O                                                                CH.sub.3                                                                               i-C.sub.3 H.sub.7                                                                      m.p. 112°-113° C.                371   H   4-i-C.sub.3 H.sub.7 O                                                                C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                        n.sub. D.sup. 20 1.5649                        372   H   4-i-C.sub.3 H.sub.7 O                                                                i-C.sub.3 H.sub.7                                                                      i-C.sub.3 H.sub.7                                                                      m.p. 60°-61° C.                  373   H   4-i-C.sub.3 H.sub.7 O                                                                i-C.sub.3 H.sub.7                                                                      t-C.sub.4 H.sub.9                                                                      m.p. 88°-89° C.                  374   H   4-i-C.sub.3 H.sub.7 O                                                                s-C.sub.4 H.sub.9                                                                      t-C.sub.4 H.sub.9                                                                      n.sub. D.sup. 20 1.5402                        375   H   4-i-C.sub.3 H.sub.7 O                                                                 ##STR87##                                                                              ##STR88##                                                                             m.p.141°-142° C.                 376   2-CH.sub.3                                                                         4-CH.sub.3                                                                           CH.sub.3                                                                               CH.sub.3                                                                               n.sub. D.sup. 20 1.5900                        377   2-CH.sub.3                                                                         4-CH.sub.3                                                                           CH.sub.3                                                                               i-C.sub.3 H.sub.7                                                                      n.sub. D.sup. 20 1.5674                        378   2-CH.sub.3                                                                         4-CH.sub.3                                                                           i-C.sub.3 H.sub.7                                                                      i-CH.sub.3.sup.H.sub.7                                                                 n.sub. D.sup.20 1.5589                         379   2-CH.sub.3                                                                         4-CH.sub.3                                                                           i-C.sub.3 H.sub.7                                                                      t-C.sub.4 H.sub.9                                                                      m.p. 99°-100° C.                 380   2-CH.sub.3                                                                         4-CH.sub.3                                                                           s-C.sub.4 H.sub.9                                                                      t-C.sub.4 H.sub.9                                                                      n.sub. D.sup. 20 1.5478                        381   2-CH.sub.3                                                                         3-CH.sub.3                                                                           CH.sub.3                                                                               CH.sub.3                                                                               m.p. 78°-79° C.                  382   2-CH.sub.3                                                                         3-CH.sub.3                                                                           C.sub.2 H.sub.5                                                                         ##STR89##                                                                             m.p. 151°-152° C.                383   2-CH.sub.3                                                                         3-CH.sub.3                                                                           i-C.sub.3 H.sub.7                                                                      i-C.sub.3 H.sub.7                                                                      m.p. 71°-72° C.                  384   2-CH.sub.3                                                                         3-CH.sub.3                                                                           i-C.sub.3 H.sub.7                                                                      t-C.sub.4 H.sub.9                                                                      m.p. 91°-92° C.                  385   2-CH.sub.3                                                                         3-CH.sub.3                                                                           s-C.sub.4 H.sub.9                                                                      t-C.sub.4 H.sub.9                                                                      n.sub. D.sup. 20 1.5465                        386   2-CH.sub.3                                                                         3-CH.sub.3                                                                            ##STR90##                                                                             t-C.sub.4 H.sub.9                                                                      n.sub. D.sup. 20 1.5769                        387   2-CH.sub.3                                                                         4-Cl  i-C.sub.3 H.sub.7                                                                      t-C.sub.4 H.sub.9                                                                      m.p. 122°-123° C.                388   2-CH.sub.3                                                                         6-CH.sub.3                                                                           i-C.sub.3 H.sub.7                                                                      t-C.sub.4 H.sub.9                                                                      m.p. 103°-104°  C.               389   2-CH.sub.3                                                                         6-CH.sub.3                                                                           CH.sub.3                                                                               CH.sub.3                                                                               n.sub. D.sup. 20 1.5967                        390   2-CH.sub.3                                                                         6-CH.sub.3                                                                           C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                        m.p. 77°-78° C.                  391   2-C.sub.2 H.sub.5                                                                  6-C.sub.2 H.sub.5                                                                    CH.sub.3                                                                               CH.sub.3                                                                               m.p. 88°-89° C.                  392   2-C.sub.2 H.sub.5                                                                  6-C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                        n.sub. D.sup. 20 1.5644                        393   2-C.sub.2 H.sub.5                                                                  6-C.sub.2 H.sub.5                                                                    CH.sub.3                                                                               i-C.sub.3 H.sub.7                                                                      m.p. 106°-107° C.                394   2-C.sub.2 H.sub.5                                                                  6-C.sub.2 H.sub.5                                                                    CH.sub.2CHCH.sub.2                                                                     CH.sub.2CHCH.sub.2                                                                     n.sub. D.sup. 20 1.5583                        395   2-C.sub.2 H.sub.5                                                                  6-C.sub.2 H.sub.5                                                                    i-C.sub.3 H.sub.7                                                                      i-C.sub.3 H.sub. 7                                                                     m.p. 89°-90° C.                  396   2-Cl                                                                               4-Cl  CH.sub.3                                                                               i-C.sub.3 H.sub.7                                                                      m.p. 109°-111° C.                397   2-Cl                                                                               4-Cl  C.sub.2 H.sub.5                                                                        t-C.sub.4 H.sub.9                                                                      m.p. 110°-112° C.                398   2-Cl                                                                               4-Cl  i-C.sub.3 H.sub.7                                                                      i-C.sub.3 H.sub.7                                                                      m.p. 121°-123°  C.               399   2-Cl                                                                               4-Cl  i-C.sub.3 H.sub.7                                                                      t-C.sub.4 H.sub.9                                                                      m.p. 130°-132° C.                400   2-Cl                                                                               4-Cl  s-C.sub.4 H.sub.9                                                                      s-C.sub.4 H.sub.9                                                                      n.sub. D.sup. 25 1.5634                        401   2-Cl                                                                               4-Cl  s-C.sub.4 H.sub.9                                                                      t-C.sub.4 H.sub.9                                                                      n.sub. D.sup. 20 1.5602                        402   2-Cl                                                                               3-Cl  i-C.sub.3 H.sub.7                                                                      i-C.sub.3 H.sub.7                                                                      m.p. 93°-94° C.                  403   3-Cl                                                                               5-Cl  CH.sub.3                                                                               CH.sub.3                                                                               m.p. 145°-147° C.                404   3-Cl                                                                               5-Cl  C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                        m.p. 100°-102° C.                405   3-Cl                                                                               5-Cl  n-C.sub.3 H.sub.7                                                                      i-C.sub.3 H.sub.7                                                                      m.p. 80°-82° C.                  406   3-Cl                                                                               5-Cl  i-C.sub.3 H.sub.7                                                                      i-C.sub.3 H.sub.7                                                                      m.p. 81°-83° C.                  407   3-Cl                                                                               5-Cl  i-C.sub.3 H.sub.7                                                                      t-C.sub.4 H.sub.9                                                                      m.p. 113°-115° C.                408   3-Cl                                                                               5-Cl                                                                                  ##STR91##                                                                             i-C.sub.3 H.sub.7                                                                      m.p. 90°-92° C.                  409   3-Cl                                                                               5-Cl  i-C.sub.3 H.sub.7                                                                      t-C.sub.8 H.sub.17                                                                     m.p. 78°-81° C.                  410   3-Cl                                                                               5-Cl  n-C.sub.6 H.sub.13                                                                     i-C.sub. 3 H.sub.7                                                                     n.sub. D.sup. 23 1.5699                        411   3-Cl                                                                               5-Cl  s-C.sub.4 H.sub.9                                                                      s-C.sub.4 H.sub.9                                                                      n.sub. D.sup. 19 1.5822                        412   3-Cl                                                                               5-Cl  CH.sub.2CHCH.sub.2                                                                     i-C.sub.3 H.sub.7                                                                      n.sub. D.sup. 19.5 1.5962                      413   3-Cl                                                                               4-Cl  C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                        m.p. 86°-88° C.                  414   3-Cl                                                                               4-Cl  n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                      n.sub. D.sup. 20 1.5848                        415   3-Cl                                                                               4-Cl  i-C.sub.3 H.sub.7                                                                      i-C.sub.3 H.sub.7                                                                      m.p. 104°-107° C.                416   3-Cl                                                                               4-Cl  i-C.sub.3 H.sub.7                                                                      t-C.sub.4 H.sub.9                                                                      m.p. 114.5°-117.5° C.            417   3-Cl                                                                               4-Cl  n-C.sub.3 H.sub.7                                                                      s-C.sub.4 H.sub.9                                                                      n.sub. D.sup.19 1.5772                         418   3-Cl                                                                               4-Cl  C.sub.2 H.sub.5                                                                        t-C.sub.4 H.sub.9                                                                      m.p. 105°-107° C.                419   3-Cl                                                                               4-Cl  C.sub.2 H.sub.5                                                                        i-C.sub.4 H.sub.9                                                                      n.sub. D.sup. 19 1.5912                        420   3-Cl                                                                               4-Cl  n-C.sub.3 H.sub.7                                                                      i-C.sub.4 H.sub.9                                                                      n.sub. D.sup. 19 1.5769                        421   3-Cl                                                                               4-Cl  CH.sub.2CHCH.sub.2                                                                     i-C.sub.3 H.sub.7                                                                      n.sub. D.sup. 19 1.5920                        422   3-Cl                                                                               4-Cl                                                                                  ##STR92##                                                                             i-C.sub.3 H.sub.7                                                                      n.sub. D.sup. 19 1.6156                        423   3-Cl                                                                               4-Cl                                                                                  ##STR93##                                                                              ##STR94##                                                                             m.p. 118°-120 ° C.               424   3-Cl                                                                               4-Cl  CH.sub.3                                                                               i-C.sub.3 H.sub.7                                                                      m.p. 145°-147° C.                425   3-Cl                                                                               4-Cl  i-C.sub.3 H.sub.7                                                                       ##STR95##                                                                             m.p. 127°-128° C.                426   2-Cl                                                                               5-Cl  C.sub.2 H.sub.5                                                                        t-C.sub.4 H.sub.9                                                                      m.p. 91°-92° C.                  427   2-Cl                                                                               5-Cl  i-C.sub.3 H.sub.7                                                                      t-C.sub.4 H.sub.9                                                                      m.p. 145°-146° C.                428   2-Cl                                                                               5-Cl  s-C.sub.4 H.sub.9                                                                      t-C.sub.4 H.sub.9                                                                      m.p. 111°-112° C.                429   2-Cl                                                                               5-Cl                                                                                  ##STR96##                                                                              ##STR97##                                                                             m.p. 119°-120° C.                430   2-Cl                                                                               3-Cl  C.sub.2 H.sub.5                                                                        t-C.sub.4 H.sub.9                                                                      m.p. 144°-145° C.                431   3-CH.sub.3                                                                         4-CH.sub.3                                                                           i-C.sub.3 H.sub.7                                                                      i-C.sub.3 H.sub.7                                                                      m.p. 66°-67° C.                  432   3-CH.sub.3                                                                         4-CH.sub.3                                                                           i-C.sub.3 H.sub.7                                                                      t-C.sub.4 H.sub.9                                                                      m.p. 109°-110° C.                433   3-CH.sub.3                                                                         4-CH.sub.3                                                                           s-C.sub.4 H.sub.9                                                                      t-C.sub.4 H.sub.9                                                                      m.p. 92°-93° C.                  __________________________________________________________________________

the compounds represented by the formula (I) exhibit strong physiological activity against insects, particularly larvae. The larva treated with the compound or ingested the diet treated with the compound dies from abnormal moulting. The insects sensitive to the compound (I) are those of, for example, Hemiptera, Coleoptera, Diptera, Lepidoptera and Orthoptera. Further, many of the compounds (I) have activity to mites; some of them retain miticidal activity to citrus red mite (Panonychus citri McGregor) and two-spotted spider mite (Tetranychus urticae Koch) even at a concentration of 1,000 ppm, the mortality being 80% or more. Accordingly, the compound of this invention is useful as a physiologically active substance to control the pests by applying to plants, grains and others to protect them from injuries inflicted by the above-noted insects and mites.

For instance, the compound of this invention is useful as an active substance to protect rice, corn an other cereals, vegetables, flowers and ornamental plants, tree, cotton, fruit trees, timbers, harvested grains, grasses, lawns and wood products from the attack of pests. The compound is also useful in controlling the insect pests undesirable for life-environment such as mosquitos and flies. It is particularly useful in controlling paddy field pests such as, for example, brown planthopper (Nilaparvata lugens Stal), smaller brown planthopper (Laodelphax striatellus Fall'en), white-backed planthopper (Sogatella furcifera Horvath), green rice leafhopper (Nephotettix cincticeps Uhler) and other plant- and leafhoppers.

Further, as compared with conventional insecticides such as phosphorus compounds and carbamate compounds, the compound of this invention is far lower in mammalian acute toxicity and, hence, is far safer. For example, 2-t-butylimino-3-isopropyl-5-phenyltetrahydro-1,3,5-thiadiazin-4-one (compound No. 145) and 2-t-butylimino-3-isopropyl-5-p-tolyltetrahydro-1,3,5-thiadiazin-4-one (compound No. 318) have LD₅₀ (mice, male) of 10,000 mg/kg or higher. Many other compounds of this invention have LD₅₀ (mice, male) of 5,000 mg/kg or higher. As compared with conventional phosphorus insecticides and carbamate insecticides, the compound of this invention exhibits insecticidal activity at lower concentrations, although the activity value varies with particular target insect. For instance, when the mortality in 7 days after spraying the compound on 5th-instar larvae of brown planthopper is compared, 1-naphthyl N-methylcarbamate (commercial insecticide NAC) showed a mortality of only 30% at 200 ppm concentration, whereas the compound of this invention, for example compound No. 145 or No. 318, showed a mortality of 100% at 100 ppm concentration.

This invention provides also the technique for eradicating or controlling injurious insectes and mites on the basis of physiological activity of the compound of this invention. In one of the embodiments of the invention, the compound is directly applied as such to the objects to be protected or to the pests to be controlled (undiluted spray). For instance, the compound of this invention in the form of liquid of 95% or higher purity can be sprayed from an aeroplane, forming a fog of extremely fine liquid particles. The compound of this invention can also be used in treating ponds and pools inhabited by larvae or treating environmental water or irrigation water grown with a host to render the inhabitation environment or the feed (host) toxic to larvae.

However, as is customary in the art, the compound of this invention is applied, in most of the cases, in the form suitable for use by supporting on or diluted with an inert carrier and, if necessary, admixing with auxiliary agents to eradicate or control injurious insects and mites by the physiological activity of the compound.

General suggestions regarding the formulation of insecticidal compositions based on the compound of this invention are described below.

The compound of this invention is blended with a suitable proportion of a suitable inert carrier and, if necessary, auxiliary agents to allow the compound to dissolve, disperse, suspend, mix, impregnate, adsorb or adhere and formed into a suitable preparation such as, for example, solution, suspension, emulsifiable concentrate, oil spray, wettable powder, dust, granule, tablet, pellet, paste or aerosol.

The inert carrier may be solid, liquid or gas. The materials for the solid carrier include plant powders such as, for example, soybean flour, grain flour, wood flour, bark flour, sawdust, tobacco stalk flour, walnut shell flour, wheat bran, powdered cellulose, and extraction residue of plants; fibrous materials such as paper, corrugated fiberboard, and waste cloth; synthetic polymers such as powdered synthetic resins and polymer granules (for example, urea-formaldehyde polymer); inorganic or mineral substances in the form of powder or granule of a suitable particle size such as clays (for example, kaolin, bentonite and acid clay), talcs (for example, talc and pyrophillite), silicic materials (for example, diatomaceous earth, silica sand, mica, synthetic silicates, finely dispersed synthetic silicic acid, etc.), powdered sulfur, activated carbon, pumice, calcined diatomaceous earth, ground brick, fly ash, sand, calcium carbonate and calcium phosphate; chemical fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea and ammonium chloride; compost, sodium sulfate, sugars and other soluble substances. These solid carriers are used each alone or in mixtures of two or more. Materials for the liquid carrier are selected from not only solvents for the active compound but also nonsolvents which can disperse the active compound in the presence of a suitable auxiliary agent. Such liquid materials are used each alone or in mixtures of two or more. Examples are water, alcohols (for example, methanol, ethanol, butanol and ethylene glycol), ketones (for example, acetone, methyl ethyl ketone, diisobutyl ketone and cyclohexanone), ethers (for example, ethyl ether, dioxane, Cellosolves, dipropyl ether and tetrahydrofuran), aliphatic hydrocarbons (for example, gasoline and mineral oils), aromatic hydrocarbons (for example, benzene, xylene, solvent naphtha, and alkylnaphthalenes), halogenated hydrocarbons (for example, dichloroethane, chlorobenzenes and carbon tetrachloride), esters (for example, ethyl acetate, dibutyl phthalate and dioctyl phthalate), acid amides (for example, diethylformamide, and dimethylformamide), nitriles (for example, acetonitrile) and dimethyl sulfoxide. Gaseous carriers include Freons and other aerosol propellants which are gas under ordinary conditions.

The auxiliary agents include the following materials which are used in accordance with the purpose of use. Combinations of two or more auxiliary agents are frequently used and in some cases no auxiliary agent is used. Surface active agents are used to emulsify, disperse, solubilize and/or wet the active compound. Examples are polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl ethers, polyoxyethylene higher fatty acid esters, polyoxyethylene resin acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, alkylarylsulfonates, naphthalenesulfonic acid condensation products, ligninsulfonate, and higher alcohol sulfate esters. The following substances are used as dispersion stabilizers, spreaders and binders for the active compound: casein, gelatin, starch, alginic acid, methylcellulose, carboxymethylcellulose, gum arabic, polyvinyl alcohol, dry-distilled wood turpentine, rice bran oil, bentonite and ligninsulfonates.

For the purpose of improving the flow property of solid preparations, may be used waxes, stearates and alkyl phosphates. Naphthalenesulfonates and polyphosphates are used as peptizing agents for dispersions. Defoamers such as silicone oil may also be included in the formulation.

The proportion of the active compound in the insecticidal formulation may be varied as required. Suitable proportion of the active compound is generally 0.5 to 20% by weight in dust or granule preparations and 0.1 to 90% by weight in emulsifiable concentrates and wettable powders.

For the purpose of eradicating various insect pests or protecting plants from the attack of various pests, the insecticidal preparation of this invention is used as such or after being suitably diluted with or suspended in water or other media and an effective quantity of the preparation is applied to the plants or environment thereof or to the area inhabited by insect pests. For instance, in order to control the insect pests inhabiting a padding field, the insecticidal preparation of this invention is applied to leaves and stems of rice plant or to the paddy soil or water of the submerged paddy field.

Application rate of the insecticidal preparation of this invention varies depending on various factors such as, for example, the type of target insect, condition and trend of emergence of pests, weather, environmental conditions, form of the insecticidal preparation, mode of application, site being applied, and time of the year. In the case of emulsifiable concentrate and wettable powder, which are applied generally in liquid form, a general practice is to dilute to a final concentration of 0.001% by weight or higher in terms of active ingredient to prepare a spray preparation. Dust and granule are generally applied at a rate of 1 to 10 kg per 10 ares. However, the above-noted application rates do not limit the scope of this invention.

The insecticidal preparation of this invention can be applied, if necessary, in admixture with or jointly with other pesticides, fertilizers, plant nutrients, and plant growth regulators. Examples of insecticides usable in admixture with the insecticide of this invention are:

O,o-dimethyl O-(4-nitro-3-methylphenyl) thiophosphate (Phenitrothion)

O,o-dimethyl O-(3-methyl-4-methylthiophenyl) thiophosphate (Baycid)

O,o-dimethyl S-(carbethoxyphenylmethyl) dithiophosphate (Elsan)

O,o-diethyl O-(2-isopropyl-4-methylpyrimidyl-6) thiophosphate (Diazinon)

O,o-dimethyl 2,2,2-trichloro-1-hydroxyethyl phosphonate (Dipterex)

O-ethyl O-p-cyanophenyl phenylphosphonothioate (Surecide)

O-ethyl O-p-nitrophenyl phenylthiophosphonate (EPN)

O,o-dipropyl O-4-methylthiophenylphosphate (Propaphos)

O,o-dimethyl S-phthalimidomethyl dithiophosphate (Imidan)

O,o-dimethyl O-dichlorovinyl phosphate (DDVP)

O,o-dimethyl S-(N-methylcarbamoylmethyl) dithiophosphate (dimethoate)

O,o-dimethyl S-(1,2-dicarbethoxyethyl) dithiophosphate (malathon)

1-Naphthyl N-methylcarbamate (NAC)

m-Tolyl N-methylcarbamate (MTMC)

2-isopropoxyphenyl N-methylcarbamate (PHC)

Ethyl N-(diethyl-dithiophosphorylacetyl)-N-methylcarbamate (Mecarbam)

3,4-Xylyl N-methylcarbamate (MPMC)

2-s-Butylphenyl N-methylcarbamate (BPMC)

2-isopropylphenyl N-methylcarbamate (MIPC)

2-chlorophenyl N-methylcarbamate (CPMC)

3,5-xylyl N-methylcarbamate (XMC)

2-(1,3-dioxolan-2-yl)phenyl N-methylcarbamate (Dioxacarb)

3-t-Butylphenyl N-methylcarbamate (Terbam)

4-Diallylamino-3,5-dimethylphenyl N-methylcarbamate (APC)

S-methyl-N-(methylcarbamoyloxy) thioacetoimidate (Methomil)

N-(2-methyl-4-chlorophenyl)-N,N-dimethylformamidine hydrochloride (chlorphenamidine)

1,3-bis(Carbamoylthio)-2-(N,N-dimethylamino)propane hydrochloride (Cartap)

Diisopropyl-1,3-dithiolan-2-ylidene malonate (Isoprothiolan)

N-[[(4-chlorophenyl)amino]carbonyl]-2,6-difluorobenzamide (Diflubenzuron)

O,o-dimethyl-S-[2-(isopropylthio)ethyl]phosphorodithioate (Isothioate)

O,o-diethyl-S-[2-(ethylthio)ethyl]-phosphorodithioate (Disulfoton)

2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methylcarbamate (Carbofuran)

EXAMPLE 1

2-Methylimino-3-phenyl-5-isopropyltetrahydro-1,3,5-thiadiazin-4-one (compound No. 66). ##STR98##

In 50 ml of benzene, were dissolved 3.4 g (0.02 mole) of N-isopropyl-N-chloromethylcarbamoyl chloride and 3.3 g (0.02 mole) of 1-methyl-3-phenylthiourea. The resulting solution was heated under reflux with stirring for 2 hours. After cooling, the precipitated crystals were collected by filtration, washed with benzene and dissolved in 200 ml of water. The resulting aqueous solution was admixed with 20 ml of saturated aqueous sodium carbonate solution and extracted with 100 ml of benzene. The benzene layer was washed with water, dried, and concentrated under reduced pressure to obtain crystals which were recrystallized from isopropyl alcohol. M.p. 174°-176° C.; yield 2.1 g (40%).

NMR(CDCl₃)δ; 1.19(d. 6H), 3.00(S. 3H), 4.42(S. 2H), 4.30-4.80(m. 1H), 7.0-7.6(m. 5H)

EXAMPLE 2

2-p-Tolylimino-3-methyl-5-t-butyl-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 72): ##STR99##

In 50 ml of toluene, were dissolved 3.7 g (0.02 mole) of N-t-butyl-N-chloromethylcarbamoyl chloride and 3.6 g (0.02 mole) of 1-methyl-3-p-tolylthiourea. The resulting solution was heated under reflux for 2 hours. The precipitated crystals were collected by filtration and washed with acetone (m.p. 189°-190° C. decomp.). The crystals were dissolved in 100 ml of water, admixed with 10 ml of a 20% sodium hydroxide solution, and extracted with 50 ml of benzene. The crystals obtained on removal of the benzene under vacuum were recrystallized from isopropyl alcohol. Yield 4.3 g (73%); m.p. 113°-115° C.

NMR(CDCl₃)δ: 1.48(S. 9H), 2.30(S. 3H), 3.35(S. 3H), 4.48(S. 2H), 6.65-7.25(m. 4H)

In a similar manner, 2-(2-methyl-4-chloro)-phenylimino-3-methyl-5-isopropyl-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 67): ##STR100## was obtained from 3.4 g of N-isopropyl-N-chloromethylcarbamoyl chloride and 4.2 g of 1-methyl-3-(2-methyl-4-chloro)phenylthiourea. m.p. 91°-92° C.; yield 3.2 g.

NMR(CDCl₃)δ: 1.20(d. 6H), 2.10(S. 3H), 3.45(S. 3H), 4.30(S. 2H), 4.45-4.95 (m. 1H), 6.55-7.20(m. 3H)

EXAMPLE 3

2-t-Butylimino-3-phenyl-5-t-butyl-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 77): ##STR101##

In 50 ml of acetone, were dissolved 3.7 g (0.02 mole) of N-t-butyl-N-chloromethylcarbamoyl chloride and 3.9 g (0.02 mole) of 1-t-butyl-3-phenylthiourea. While stirring, 2.8 g of powdered potassium carbonate was added to the resulting solution and heated under reflux for 2 hours. The reaction mixture was poured into water and extracted with 50 ml of benzene. The benzene layer was washed with water, dried, and concentrated under reduced pressure. The crystals obtained were recrystallized from isopropyl alcohol. Yield 4.1 g (66%); m.p. 133°-134° C.

NMR(CDCl₃)δ: 1.10(S. 9H), 1.46(S. 9H), 4.60(S. 2H), 7.0-7.4(m. 5H)

EXAMPLE 4

2-Ethylimino-3-o-tolyl-5-t-butyl-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 80): ##STR102##

In 50 ml of benzene, were dissolved 3.7 g (0.02 mole) of N-t-butyl-N-chloromethylcarbamoyl chloride and 3.8 g of 1-ethyl-3-O-tolylthiourea. While stirring, 8 g of a 20% sodium hydroxide solution was added to the above solution and stirring was continued for further 4 hours at 30° to 50° C. The reaction mixture was poured into water and extracted with 50 ml of benzene. The benzene layer was washed with water and dried. The crystals obtained on removal of the benzene by distillation were recrystallized from isopropyl alcohol. Yield 3.8 g (63%); m.p. 157°-158° C.

EXAMPLE 5

2-Phenylimino-3-phenyl-5-t-butyl-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 78): ##STR103##

In a mixture of 50 ml of benzene and 10 ml of dimethyl sulfoxide, were dissolved 3.7 g (0.02 mole) of N-t-butyl-N-chloromethylcarbamoyl chloride and 4.6 g of 1,3-diphenylthiourea. While stirring at room temperature, 6.1 g of 1,8-diazabicyclo[5,4,0]-7-undecene was added to the above solution and stirring was continued for further 5 hours. The reaction mixture was poured into water and extracted with benzene. The benzene layer was washed with water and dried. The crystals obtained on removal of the benzene by distillation were recrystallized from isopropyl alcohol. Yield 4.4 g (65%); m.p. 142°-143° C.

EXAMPLE 6

2-Isopropylimino-3-isopropyl-5-methyl-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 1): ##STR104##

To 2.8 g (0.02 mole) of N-methyl-N-chloromethylcarbamoyl chloride dissolved in 50 ml of benzene, was added 3.2 g (0.02 mole) of 1,3-diisopropylthiourea. The mixture was heated under reflux with stirring for 2 hours. After cooling, 10 g of a 30% potassium hydroxide solution and 50 ml of benzene were added to the mixture and the mixture was shaken thoroughly. The separated benzene layer was washed with water, dried, and the benzene was distilled off under vacuum. The crystals thus obtained were recrystallized from ether. Yield 3.0 g (66%); m.p. 76°-77° C.

NMR(CDCl₃)δ: 1.15(d. 6H), 1.40(d. 6H), 3.10(S. 3H) 4.45(S. 2H), 4.50-4.80(m. 1H), 3.30-3.80(m. 1H)

EXAMPLE 7

2-Ethylimino-3,5-diethyl-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 7): ##STR105##

To a mixture of 3.1 g (0.02 mole) of N-ethyl-N-chloromethylcarbamoyl chloride and 2.6 g (0.02 mole) of 1,3-diethylthiourea dissolved in 50 ml of benzene, was added with stirring at room temperature 8 g of a 20% sodium hydroxide solution. After stirring for 5 hours, the reaction mixture was poured into water and extracted with 50 ml of benzene. The benzene layer was washed with water, dried, and the benzene was distilled off under vacuum. The oily substance thus obtained was crystallized from ether. Yield 2.8 g (66%); m.p. 68°-70° C.

NMR(CDCl₃)δ; 1.20(t. 9H), 3.20-3.70(m. 4H), 3.75-4.10(q. 2H), 4.40(S. 2H)

EXAMPLE 8

2-Isopropylimino-3-methyl-5-isopropyl-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 18): ##STR106##

In 50 ml of benzene, were dissolved 3.4 g (0.02 mole) of N-isopropyl-N-chloromethylcarbamoyl chloride and 2.6 g (0.02 mole) of 1-isopropyl-3-methylthiourea. The solution was heated under reflux for 2 hours. After cooling, the precipitated crystals (m.p. 198°-200° C. decomp.) were collected by filtration, washed with a small quantity of acetone, again dissolved in 100 ml of water, admixed with 10 ml of a 30% potassium hydroxide solution, and extracted with 100 ml of benzene. The benzene layer was washed with water, dried, and freed from the benzene by distillation. The crystals thus obtained were recrystallized from ether. Yield 3.8 g (83%).

NMR(CDCl₃)δ: 1.10(d. 6H), 1.16(d. 6H), 3.20(S. 3H), 4.33(S. 2H), 4.40-4.85(m. 1H), 3.30-3.70(m. 1H)

EXAMPLE 9

2-Methylimino-3-methyl-5-t-butyl-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 31): ##STR107##

In 50 ml of toluene, were dissolved 3.7 g (0.02 mole) of N-t-butyl-N-chloromethylcarbamoyl chloride and 2.0 g (0.02 mole) of 1,3-dimethylthiourea. The solution was heated under reflux with stirring for one hour. After cooling, the precipitated crystals (m.p. >220° C. decomp.) were collected by filtration, washed with a small quantity of acetone, dissolved again in 100 ml of water, admixed with 10 ml of a 20% sodium hydroxide solution, and extracted with 50 ml of benzene. The benzene layer was dried and concentrated under reduced pressure to obtain 3.5 g (83% yield) of crystals melting at 51°-52° C.

NMR(CDCl₃)δ: 1.47(S. 9H), 3.03(S. 3H), 3.14(S. 3H), 4.53(S. 2H)

EXAMPLE 10

2-t-Butylimino-3-benzyl-5-t-butyl-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 47): ##STR108##

In 50 ml of xylene, were dissolved 3.7 g (0.02 mole) of N-t-butyl-N-chloromethylcarbamoyl chloride and 4.4 g (0.02 mole) of 1-t-butyl-3-benzylthiourea. To the solution, while being stirred at room temperature, was added 8 g of a 30% potassium hydroxide solution. The mixture was stirred for further 4 hours while heating at 30° to 50° C. The reaction mixture was poured into water and extracted with 100 ml of benzene. The benzene layer was washed with water, dried, and the benzene was removed by distillation. The oily substance thus obtained was crystallized from ether. Yield 4.5 g (68%); m.p. 75°-76° C.

EXAMPLE 11

2-Methylimino-3-methyl-5-benzyl-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 54): ##STR109##

A mixture of 4.4 g (0.02 mole) of N-benzyl-N-chloromethylcarbamoyl chloride and 2.0 g (0.02 mole) of 1,3-dimethylthiourea was dissolved in 50 ml of ethyl alcohol and heated under reflux with stirring for 2 hours. After addition of 20 ml of a saturated aqueous potassium carbonate solution, the mixture was extracted with 100 ml of benzene. The benzene layer was washed with water, dried, and freed from the benzene by distillation under reduced pressure to obtain 4.0 g of crude crystals which were recrystallized from ether. Yield 3.2 g (63%); m.p. 93°-95° C.

EXAMPLE 12

2-t-Butylimino-3-methyl-5-(1,1,3,3-tetramethyl)-butyl-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 63): ##STR110##

In a mixture of 50 ml of benzene and 10 ml of dimethyl sulfoxide, were dissolved 4.8 g (0.02 mole) of N-(1,1,3,3-tetramethyl)butyl-N-chloromethylcarbamoyl chloride and 2.9 g (0.02 mole) of 1-methyl-3-t-butylthiourea. To the solution, was added with stirring 2.8 g of powdered potassium carbonate and stirring was continued for further 4 hours at 30° to 50° C. The reaction mixture was poured into water and extracted with 50 ml of benzene. The benzene layer was washed with water, dried, and the benzene was removed by distillation under reduced pressure. The oily substance thus obtained was crystallized from ether. Yield 5.1 g (82%); m.p. 91°-93° C.

NMR(CDCl₃)δ: 0.97 (S. 9H), 1.20 (S. 9H), 1.50 (S. 6H), 1.90 (S. 2H), 3.18 (S. 3H), 4.54 (S. 2H)

EXAMPLE 13

2-s-Butylimino-3H-5-t-butyl-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 107): ##STR111##

To 1.4 g (0.01 mole) of s-butylthiourea dissolved in 20 ml of acetone, was added 8 g of a 15% potassium hydroxide solution. To the resulting mixture, was added dropwise 1.9 g of N-chloromethyl-N-t-butylcarbamoyl chloride with stirring at room temperature. After stirring for 30 minutes, the reaction mixture was poured into water and extracted with 100 ml of benzene. The benzene layer was dried and concentrated to obtain crude crystals which were recrystallized from ether-isopropyl alcohol. There were obtained 1.6 g (63% yield) of crystals melting at 98°-100° C.

EXAMPLE 14

2-Imino-3H-5-t-butyl-tetrahydro-1,3,5-thiadiazin-4(3H)-one (compound No. 109): ##STR112##

To a suspension of 0.8 g (0.01 mole) of thiourea and 8 g of a 15% potassium hydroxide solution in 50 ml of benzene, was added dropwise 1.9 g (0.01 mole) of N-chloromethyl-N-t-butylcarbamoyl chloride with stirring at room temperature. After stirring for one hour at room temperature, the crystals formed were collected by filtration and recrystallized from chloroform to obtain 0.75 g (41% yield) of crystals melting at 123°-125° C.

EXAMPLE 15

2-Methylimino-3-methyl-5-phenyl-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 115): ##STR113##

In 50 ml of benzene, were dissolved 2.1 g (0.01 mole) of N-chloromethyl-N-phenylcarbamoyl chloride and 1.0 g (0.01 mole) of 1,3-dimethylthiourea. The resulting solution was heated under reflux with stirring for 3 hours. After cooling, the benzene layer was removed from the reaction mixture by decantation. The residual layer was washed with a small quantity of benzene. The residue (hydrochloride, m.p. 168°-170° C. decomp.) was dissolved in water, admixed with 10 ml of a 10% (W/W) aqueous sodium hydroxide solution and extracted with 100 ml of benzene. The benzene layer was washed with water, dried, and freed from the benzene by distillation under reduced pressure to obtain crude crystals which were recrystallized from isopropyl alcohol. Yield 1.3 g (51%); m.p. 68°-70° C.

NMR(CDCl₃)δ: 3.15 (S. 3H), 3.30 (S. 3H), 4.80 (S. 2H), 7.33 (S. 5H)

EXAMPLE 16

2-Isopropylimino-3-methyl-5-phenyl-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 118): ##STR114##

In 50 ml of toluene, were dissolved 2.1 g (0.01 mole) of N-chloromethyl-N-phenylcarbamoyl chloride and 1.3 g (0.01 mole) of 1-isopropyl-3-methylthiourea. To the solution, was added with stirring at room temperature 4 ml of a 20% (W/W) aqueous sodium hydroxide solution and the mixture was stirred for 6 hours. The reaction mixture was poured into water and extracted with 50 ml of benzene. The benzene layer was washed with water, dried and concentrated to obtain crude crystals which were recrystallized from isopropyl alcohol. Yield 1.3 g (50%); m.p. 72°-73.5° C.

NMR(CDCl₃)δ: 1.15 (d. 6H), 3.29 (S. 3H), 3.25-3.85 (m. 1H), 4.73 (S. 2H), 7.28 (S. 5H)

EXAMPLE 17

2-Isopropylimino-3-isopropyl-5-phenyltetrahydro-1,3,5-thiadiazin-4-one (compound No. 144): ##STR115##

In 50 ml of benzene, were dissolved 2.1 g (0.01 mole) of N-chloromethyl-N-phenylcarbamoyl chloride and 1.6 g (0.01 mole) of 1,3-diisopropylthiourea. The solution was heated under reflux with stirring for 2 hours. The crystals which were formed were collected by filtration. The crystals (hydrochloride, m.p. 188°-190° C. decomp.) were washed with a small quantity of cold acetone, dissolved in water, admixed with 2.8 g of powdered sodium carbonate, and extracted with 100 ml of benzene. The benzene layer was washed with water, dried, and the benzene was removed by distillation to obtain crude crystals which were recrystallized from isopropyl alcohol. Yield 1.8 g (62%); m.p. 92°-94° C.

NMR spectrum (CDCl₃)δ: 1.15 (d. 6H), 1.49 (d. 6H), 3.25-3.68 (m. 1H), 4.82-4.99 (m. 1H), 4.75 (S. 2H), 7.30 (S. 5H).

IR spectrum (KBr): vc=0 1660 cm⁻¹

EXAMPLE 18

2-t-Butylimino-3-isopropyl-5-phenyl-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 145): ##STR116##

In a mixture of 50 ml of acetone and 10 ml of dimethylformamide, were dissolved 2.1 g (0.01 mole) of N-chloromethyl-N-phenylcarbamoyl chloride and 1.7 g (0.01 mole) of 1-isopropyl-3-t-butylthiourea. To the solution, while stirring at room temperature, was added 4 ml of a 30% (W/W) aqueous potassium hydroxide solution and the mixture was stirred for further 5 hours. The reaction mixture was poured into water and extracted with 100 ml of benzene. The benzene layer was washed with water, dried, and concentrated to obtain a viscous oily substance which was crystallized from isopropyl alcohol. Yield 2.0 g (65%); m.p. 104°-106° C.

NMR(CDCl₃)δ: 1.33 (S. 9H), 1.45 (d. 6H), 4.70 (S. 2H), 4.32-5.00 (m. 1H), 7.30 (S. 5H)

EXAMPLE 19

2-Isopropylimino-3-isobutyl-5-phenyl-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 149): ##STR117##

In a mixture of 50 ml of tetrahydrofuran and 10 ml of dimethyl sulfoxide, were dissolved 2.1 g (0.01 mole) of N-chloromethyl-N-phenylcarbamoyl chloride and 1.7 g (0.01 mole) of 1-isopropyl-3-isobutylthiourea. To the solution, while stirring at room temperature, was added 2.1 g of triethylamine and the mixture was stirred for further 6 hours. The reaction mixture was poured into water and extracted with 100 ml of benzene. The benzene layer was washed with water, dried, and concentrated to obtain a viscous oily substance which was crystallized from isopropyl alcohol. Yield 2.4 g (78%); m.p. 80°-82° C.

NMR(CDCl₃)δ: 0.90 (d. 6H), 1.15 (d. 6H), 1.70-2.30 (m. 1H), 3.35-3.75 (m. 1H), 4.05 (d. 2H), 4.75 (S. 2H), 7.30 (S. 5H)

EXAMPLE 20

2-t-Butylimino-3-cyclohexyl-5-phenyl-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 155): ##STR118##

In 50 ml of ether, were dissolved 2.1 g (0.01 mole) of N-chloromethyl-N-phenylcarbamoyl chloride and 2.1 g (0.01 mole) of 1-cyclohexyl-3-t-butylthiourea followed by 1.6 g of pyridine. The resulting solution was stirred for 4 hours at room temperature. The reaction mixture was poured into water and extracted with 100 ml of benzene. The benzene layer was washed with water, dried, and concentrated to obtain an oily substance which was crystallized from isopropyl alcohol. Yield 1.6 g (45%); m.p. 86°-89° C.

NMR(CDCl₃)δ: 1.35 (S. 9H), 1.0-2.5 (m. 11H), 4.75 (S. 2H), 7.33 (S. 5H)

EXAMPLE 21

2-Benzylimino-3-methyl-5-phenyl-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 121): ##STR119##

In 20 ml of a 6% (W/W) aqueous potassium hydroxide solution, was suspended 1.8 g (0.01 mole) of 1-methyl-3-benzylthiourea. To the suspension, was added with stirring at room temperature 2.1 g of N-chloromethyl-N-phenylcarbamoyl chloride and the mixture was vigorously stirred for one hour at room temperature. The reaction mixture was poured into water and extracted with 100 ml of benzene. The benzene layer was washed with water, dried, and concentrated to obtain an oily substance which was crystallized from isopropyl alcohol. Yield 2.0 g (63%); m.p. 90°-92° C.

NMR(CDCl₃)δ: 3.35 (S. 3H), 4.50 (S. 2H), 4.65 (S. 2H), 7.0-7.5 (m. 10H)

EXAMPLE 22

2-n-Octylimino-3-methyl-5-phenyl-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 122): ##STR120##

In ethyl alcohol, were dissolved 2.1 g (0.01 mole) of N-chloromethyl-N-phenylcarbamoyl chloride and 2.0 g (0.01 mole) of 1-methyl-3-n-octylthiourea. The solution was heated under reflux with stirring for 3 hours. After cooling, the reaction mixture was poured into water, admixed with 5 ml of a 20% (W/W) aqueous sodium hydroxide solution, and extracted with 100 ml of benzene. The benzene layer was washed with water, dried, and concentrated to obtain a viscous oily substance which was dissolved in 6 N hydrochloric acid and freed from the insoluble matter by extraction with benzene. The aqueous layer was made slightly alkaline by addition of a 20% (W/W) aqueous sodium hydroxide solution and extracted with 50 ml of benzene. The benzene layer was washed with water, dried, and concentrated to obtain a viscous oily substance. Yield 1.2 g (36%); n_(D) ²⁰ 1.5551.

EXAMPLE 23

2-s-Butylimino-3,5-diphenyl-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 163): ##STR121##

In a mixture of 50 ml of ethyl acetate and 10 ml of dimethyl sulfoxide, were dissolved 2.1 g (0.01 mole) of N-chloromethyl-N-phenylcarbamoyl chloride and 1.9 g (0.01 mole) of 1-s-butyl-3-phenylthiourea. To the solution, was added 1.1 g of powdered sodium carbonate and the mixture was stirred for 3 hours at 50° C. The reaction mixture was poured into water and extracted with 50 ml of ethyl acetate. The ethyl acetate layer was washed with water, dried, and concentrated to obtain crude crystals which were recrystallized from isopropyl alcohol. Yield 1.9 g (57%); m.p. 134°-135.5° C.

NMR(CDCl₃)δ: 0.5-1.5 (m. 8H), 3.0-3.5 (m. 1H), 4.85 (S. 2H), 7.25 (S. 10H)

EXAMPLE 24

2-(2-Methyl)phenylimino-3-methyl-5-phenyltetrahydro-1,3,5-thiadiazin-4-one (compound No. 124): ##STR122##

In 50 ml of benzene, were dissolved 2.1 g (0.01 mole) of N-chloromethyl-N-phenylcarbamoyl chloride and 1.8 g (0.01 mole) of 1-methyl-3-o-tolylthiourea. To the solution, while stirring at room temperature, was added 3.1 g of 1,8-diazabicyclo-[5,4,0]-7-undecene and the mixture was stirred for 4 hours. The reaction mixture was poured into water and extracted with 100 ml of benzene. The benzene layer was washed with water, dried, and concentrated to obtain crude crystals which were recrystallized from isopropyl alcohol. Yield 2.0 g (63%); m.p. 113°-114° C.

NMR(CDCl₃)δ: 2.18 (S. 3H), 3.50 (S. 3H), 4.68 (S. 2H), 7.0-7.5 (m. 9H).

EXAMPLE 25

2-Methylimino-3-(2-methyl-4-chloro)phenyl-5-phenyl-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 166): ##STR123##

In a mixture of 10 ml of benzene and 10 ml of tetrahydrofuran, were dissolved 1.4 g (1/150 mole) of N-chloromethyl-N-phenylcarbamoyl chloride and 1.4 g (1/150 mole) of 1-methyl-3-(2-methyl-4-chloro)phenylthiourea. To the solution, was added with stirring 5.5 g of a 10% (W/W) aqueous sodium hydroxide solution and the mixture was vigorously stirred for 4 hours, while maintaining the reaction temperature at 40° C. After completion of the reaction, the benzene layer was washed with water and concentrated to obtain an oily mixture of 2-methylimino-3-(2-methyl-4-chloro)phenyl-5-phenyl-tetrahydro-1,3,5-thiadiazin-4-one and 2-(2-methyl-4-chloro)phenylimino-3-methyl-5-phenyltetrahydro-1,3,5-thiadiazin-4-one.

The compound No. 166 could be separated from the above mixture in the following manner.

The above oily mixture was dissolved in 3 N hydrochloric acid and the insoluble matter was removed by washing with ethyl acetate. The aqueous layer was made slightly alkaline to precipitate crystals which were recrystallized from isopropyl alcohol-n-hexane to obtain 1.2 g (52% yield) of the compound No. 166 melting at 121°-123° C.

NMR(CDCl₃)δ: 2.18 (S. 3H), 3.07 (S. 3H: ═N--CH₃), 4.92 (S. 2H).

EXAMPLE 26

2-Methylimino-3-methyl-5-(p-chlorophenyl)tetrahydro-1,3,5-thiadiazin-4-one (compound No. 188): ##STR124##

In 50 ml of benzene, were dissolved 2.4 g (0.01 mole) of N-chloromethyl-N-(p-chlorophenyl)carbamoyl chloride and 1.0 g (0.01 mole) of 1,3-dimethylthiourea. The solution was heated under reflux for one hour. The crystals which were formed were collected by filtration and washed with acetone. The resulting white crystals (hydrochloride, m.p. 205° C.) were dissolved in water, admixed with 5 ml of a 20% sodium hydroxide solution, shaken thoroughly, and extracted with benzene. The crystals obtained on removal of the benzene by distillation were recrystallized from isopropyl alcohol to obtain 1.6 g (60% yield) of crystals melting at 98°-100° C.

EXAMPLE 27

2-Isopropylimino-3-methyl-5-(p-chlorophenyl)tetrahydro-1,3,5-thiadiazin-4-one (compound No. 189): ##STR125##

In 50 ml of benzene, were dissolved 2.4 g (0.01 mole) of N-chloromethyl-N-(p-chlorophenyl)carbamoyl chloride and 1.3 g (0.01 mole) of 1-isopropyl-3-methylthiourea. To the solution, was added dropwise with stirring 8 ml of a 10% sodium hydroxide solution and the mixture was further stirred for 4 hours at 40° C. The reaction mixture was poured into water and extracted with benzene. The benzene layer was washed with water, dried, and the benzene was removed by distillation to obtain crystals which were recrystallized from isopropyl alcohol. There were obtained 2.4 g (82% yield) of crystals melting at 106°-108° C.

NMR(CDCl₃)δ: 1.18 (d. 6H), 3.32 (S. 3H), 3.55 (m. 1H) 4.80 (S. 2H), 7.25 (S. 4H)

In a manner similar to that described above, 2.3 g (0.01 mole) of i-isopropyl-3-t-octylthiourea and 2.7 g (0.01 mole) of N-chloromethyl-N-m-trifluoromethylphenylcarbamoyl chloride were treated to obtain 2-t-octylimino-3-isopropyl-5-(m-trifluoromethylphenyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 266) as an oily substance: ##STR126## n_(D) ²⁴ 1.5089

NMR(CDCl₃)δ: 4.70 (s. 2H, ##STR127##

EXAMPLE 28

2-t-Butylimino-3-isopropyl-5-(p-chlorophenyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 196): ##STR128##

In 50 ml of benzene, were dissolved 2.4 g (0.01 mole) of N-chloromethyl-N-(p-chlorophenyl)-carbamoyl chloride and 1.7 g (0.01 mole) of 1-isopropyl-3-t-butylthiourea. After addition of 8 ml of a 15% potassium hydroxide solution, the mixture was allowed to react by heating at 40° to 50° C. with stirring for 4 hours. The reaction mixture was poured into water and extracted with benzene. The benzene layer was washed with water, dried, and the benzene was removed by distillation to obtain crude crystals which were recrystallized from ethanol. There were obtained 2.0 g (62% yield) of crystals melting at 123°-125° C.

EXAMPLE 29

2-t-Butylimino-3-benzyl-5-(p-chlorophenyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 204): ##STR129##

In 50 ml of toluene, were dissolved 2.4 g (0.01 mole) of N-chloromethyl-N-(p-chlorophenyl)-carbamoyl chloride and 2.2 g (0.01 mole) of 1-t-butyl-3-benzylthiourea. After addition of 8 ml of a 10% sodium hydroxide solution, the mixture was allowed to react by heating at 40° to 50° C. with stirring for 4 hours. The reaction mixture was washed with water and the toluene layer was dried and freed from the toluene by distillation to obtain crude crystals which were recrystallized from isopropyl alcohol. There were obtained 2.8 g (73% yield) of crystals melting at 87°-89° C.

EXAMPLE 30

2-t-Butylimino-3-ethyl-5-(m-chlorophenyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 216): ##STR130##

In 50 ml of tetrahydrofuran, were dissolved 2.4 g (0.01 mole) of N-chloromethyl-N-(m-chlorophenyl)-carbamoyl chloride and 1.6 g (0.01 mole) of 1-ethyl-3-t-butylthiourea. After addition of 8 ml of a 15% potassium hydroxide solution, the mixture was allowed to react by heating at 40° to 50° C. with stirring for 4 hours. The reaction mixture was poured into water and extracted with benzene. The benzene layer was dried and concentrated to obtain a viscous oily substance. n_(D) ²⁰ 1.5683

NMR(CDCl₃)δ: 3.90 ##STR131##

EXAMPLE 31

2-t-Butylimino-3-s-butyl-5-(m-chlorophenyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 225): ##STR132##

In 50 ml of xylene, were dissolved 2.4 g (0.01 mole) of N-chloromethyl-N-(m-chlorophenyl)-carbamoyl chloride and 1.8 g (0.01 mole) of 1-s-butyl-3-t-butylthiourea. After addition of 8 ml of a 10% sodium hydroxide solution, the mixture was allowed to react by heating at 40°-50° C. with stirring for 4 hours. The reaction mixture was washed with water, dried, and dry gaseous hydrogen chloride was introduced into this xylene solution at room temperature until no more crystals had been precipitated. The crystals were collected by filtration and washed with acetone. The crystals (hydrochloride, m.p. 186° C. decomp.) were suspended in water, admixed with 10 ml of a 15% potassium hydroxide solution, shaken well, and extracted with benzene. The benzene layer was dried and freed from the benzene by distillation to obtain 1.9 g (60% yield) of white crystals melting at 75°-76° C.

EXAMPLE 32

2-Isopropylimino-3-isopropyl-5-(o-chlorophenyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 244): ##STR133##

In 50 ml of benzene, were dissolved 2.4 g (0.01 mole) of N-chloromethyl-N-(o-chlorophenyl)-carbamoyl chloride and 1.6 g (0.01 mole) of 1,3-diisopropylthiourea. After addition of 8 ml of a 10% sodium hydroxide solution, the mixture was allowed to react by heating at 50° to 60° C. with stirring for 4 hours. The reaction mixture was washed with water, dried, and freed from the benzene by distillation to obtain crude crystals which were recrystallized from isopropyl alcohol to obtain 1.8 g (56% yield) of crystals melting at 95°-96° C.

NMR(CDCl₃)δ: 1.15 (d. 6H), 1.45 (d. 6H), 4.68 (s. 2H), 3.50 (m. 1H), 4.73 (m. 1H), 7.15 (m. 4H)

The above procedure was followed using 1.7 g (0.01 mole) of 1-isopropyl-3-t-butylthiourea to obtain white crystals (m.p. 88°-89° C.) of 2-t-butylimino-3-isopropyl-5-(o-chlorophenyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 245): ##STR134## Yield 2.3 g (70%). The crystals were dissolved in benzene and gaseous hydrogen chloride was introduced into the solution. The precipitated crystals were collected by filtration and washed with acetone to obtain crystalline hydrochloride melting at 201° C. (decomp.).

In a similar manner, 1.7 g (0.01 mole) of 1-isopropyl-3-s-butylthiourea and 2.2 g (0.01 mole) of N-chloromethyl-N-(p-fluorophenyl)-carbamoyl chloride were allowed to react to yield crystals melting at 81°-82° C. The crystals gave single spot on a thin-layer chromatogram using a hexane-acetone mixture (8:2) as developing solvent. However, the NMR spectrum revealed that the crystals were approximately 1:1 mixture of the compounds No. 361 and No. 362:

2-Isopropylimino-3-s-butyl-5-(p-fluorophenyl)-tetrahydro-1,3,5-thiadiazin-4-one: ##STR135##

NMR(CDCl₃)δ: ##STR136##

2-s-Butylimino-3-isopropyl-5-(p-fluorophenyl)-tetrahydro-1,3,5-thiadiazin-4-one: ##STR137##

NMR(CDCl₃)δ: ##STR138##

EXAMPLE 33

2-Methylimino-3-methyl-5-(p-fluorophenyl)-tetrahydro-1,3,5-thiadiazin-4-one hydrochloride (compound No. 277): ##STR139##

In 50 ml of benzene, were dissolved 1.0 g (0.01 mole) of 1,3-dimethylthiourea and 2.2 g (0.01 mole) of N-chloromethyl-N-(p-fluorophenyl)-carbamoyl chloride. The solution was heated under reflux with stirring for one hour. The oily substance obtained on removal of the benzene by distillation was dissolved in acetone and the precipitated crystals were collected by filtration and washed with acetone to obtain 2.1 g (85% yield) of white crystals of the hydrochloride melting at 221° C. (decomp.). A portion (1 g) of the crystals was dissolved in 20 ml of water, admixed with 5 ml of a 10% sodium hydroxide solution, shaken thoroughly, and extracted with benzene. The benzene layer was dried and concentrated to obtain crystals of free base melting at 105°-106° C.

In a similar manner, 1.7 g (0.01 mole) of 1-isopropyl-3-t-butylthiourea was reacted with 2.2 g (0.01 mole) of N-chloromethyl-N-(p-fluorophenyl)-carbamoyl chloride to obtain 2-t-butylimino-3-isopropyl 5-(p-fluorophenyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 282): ##STR140## in the form of hydrochloride melting at 160°-195° C. Yield 2.8 g (80%). The crystals were suspended in 20 ml of water and treated in a manner similar to that described above to obtain white crystals of the free base melting at 109°-110° C. (isopropanol). Yield 2.0 g (63%).

EXAMPLE 34

2-Isopropylimino-3-allyl-5-(m-chlorophenyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 217): ##STR141##

In 50 ml of benzene, were dissolved 2.4 g (0.01 mole) of N-chloromethyl-N-(m-chlorophenyl)-carbamoyl chloride and 1.58 g (0.01 mole) of 1-allyl-3-isopropylthiourea. After addition of 8 ml of a 10% sodium hydroxide solution to the solution, the mixture was allowed to react by heating at 40° to 50° C. with stirring for 4 hours. The reaction mixture was washed with water, dried, and concentrated to obtain a viscous oily substance (n_(D) ¹⁹ 1.5857) in a yield of 80%.

The above oily substance was dissolved in benzene and gaseous hydrogen chloride was introduced in the solution to obtain hydrochloride melting at 179° C. (decomp.).

EXAMPLE 35

2-t-Butylimino-3-isopropyl-5-(m-chlorophenyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 221): ##STR142##

In 50 ml of benzene, were dissolved 2.4 g (0.01 mole) of N-chloromethyl-N-(m-chlorophenyl)-carbamoyl chloride and 1.74 g (0.01 mole) of 1-isopropyl-3-t-butylthiourea. After addition of 8 ml of a 10% sodium hydroxide solution, the mixture was allowed to react by heating at 40° to 50° C. with stirring for 4 hours. The benzene layer was washed with water, dried, and concentrated to obtain a viscous oily substance which was crystallized from isopropyl alcohol to obtain 1.5 g (45% yield) of white crystals having a melting point of 113°-115° C. The crystals were dissolved in benzene and gaseous hydrogen chloride was passed to obtain hydrochloride melting at 152° C. (decomp.).

EXAMPLE 36

2-Cyclohexylimino-3-isopropyl-5-(o-chlorophenyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 252): ##STR143##

In 50 ml of benzene, were dissolved 2.4 g (0.01 mole) of N-chloromethyl-N-(o-chlorophenyl)-carbamoyl chloride and 2.0 g (0.01 mole) of 1-isopropyl-3-cyclohexylthiourea. After addition of 8 ml of a 10% sodium hydroxide solution, the mixture was allowed to react by heating at 40° to 50° C. with stirring for 4 hours. After completion of the reaction, the benzene layer was washed with water, dried, and concentrated to obtain a viscous oily substance which was crystallized from isopropyl alcohol-n-hexane (1:1) to obtain white crystals melting at 123°-125° C. in a yield of 22.5%.

EXAMPLE 37

2-Ethylimino-3-phenyl-5-(o-chlorophenyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 256): ##STR144##

In 50 ml of benzene, were dissolved 2.4 g (0.01 mole) of N-chloromethyl-N-(o-chlorophenyl)-carbamoyl chloride and 1.8 g (0.01 mole) of 1-ethyl-3-phenylthiourea. After addition of 8 ml of a 10% sodium hydroxide solution, the mixture was allowed to react by heating at 40° to 50° C. with stirring for 4 hours. After completion of the reaction, the benzene layer was washed with water, dried, and concentrated to obtain a viscous oily substance which was crystallized from isopropyl alcohol-n-hexane (1:1) to obtain 0.8 g (14% yield) of white crystals melting at 77°-79° C.

EXAMPLE 38

2-Isopropylimino-3-isopropyl-5-(m-trifluoromethylphenyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 265): ##STR145##

In 50 ml of benzene, were dissolved 2.7 g (0.01 mole) of N-chloromethyl-N-(m-trifluoromethylphenyl)-carbamoyl chloride and 1.6 g (0.01 mole) of 1,3-diisopropylthiourea. After addition of 8 ml of a 10% sodium hydroxide solution, the mixture was allowed to react by heating at 40° to 50° C. with stirring for 4 hours. After completion of the reaction, the benzene layer was washed with water, dried, and concentrated to obtain a viscous oily substance which was crystallized from isopropyl alcohol-n-hexane (1:1) to yield 1.3 g (36% yield) of white crystals melting at 67°-68° C.

EXAMPLE 39

2-t-Butylimino-3-isopropyl-5-(p-tolyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 318): ##STR146##

In 10 ml of tetrahydrofuran, was suspended 1.0 g (0.0028 mole) of 1,3,5-tris(p-tolyl)-hexahydro-s-triazine. The resulting suspension was added dropwise with stirring to 5 ml of ice-cooled benzene containing 0.9 g (0.0042 mole) of trichloromethyl chloroformate. After completion of the dropwise addition, the mixture was stirred for one hour at room temperature. To the mixture, was added 20 ml of benzene containing 1.4 g (0.0083 mole) of 1-isopropyl-3-t-butylthiourea. After addition of 7 ml of a 10% sodium hydroxide solution, the mixture was stirred for 4 to 6 hours at 40° to 50° C. The reaction mixture was washed with water, dried, and freed from the benzene by distillation. The crude product thus obtained was recrystallized from isopropyl alcohol to obtain 1.2 g (45% yield) of white crystals melting at 118°-120° C.

NMR(CDCl₃)δ: 4.75 (s. 2H), 4.70 (m. 1H), 2.35 (s. 3H), 1.47 (d. 6H), 1.33 (s. 9H)

EXAMPLE 40

2-Benzylimino-3-benzyl-5-(p-tolyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 321): ##STR147##

In 10 ml of tetrahydrofuran, was suspended 1.0 g (0.0028 mole) of 1,3,5-tris(p-tolyl)-hexahydro-s-triazine. The suspension was added dropwise with stirring at room temperature to 5 ml of benzene containing 0.9 g (0.0042 mole) of trichloromethyl chloroformate. Thereafter, the mixture was stirred for one hour at room temperature. To the mixture, was added 2.1 g (0.0083 mole) of 1,3-bis(benzyl)thiourea dissolved in 20 ml of benzene, then followed by 7 ml of a 10% sodium hydroxide solution. The mixture was stirred for 7 hours at room temperature. The reaction mixture was washed with water, dried, and freed from the benzene by distillation to obtain crude crystals which were recrystallized from isopropyl alcohol to yield 1.7 g (51% yield) of white crystals melting at 152°-153° C.

NMR(CDCl₃)δ: 7.2 (m. 14H), 5.32 (s. 2H, ##STR148## 4.78 (s. 2H), 4.50 (s. 2H, ═N--CH₂ --), 2.32 (s. 3H)

EXAMPLE 41

2-Isopropylimino-3-isopropyl-5-(o-tolyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 301): ##STR149##

A solution of 2.4 g (0.0067 mole) of 1,3,5-tris(o-tolyl)-hexahydro-s-triazine in 10 ml of tetrahydrofuran was added dropwise with stirring at room temperature to 10 ml of benzene containing 2.0 g (0.01 mole) of trichloromethyl chloroformate. Thereafter, the mixture was stirred for 30 minutes at 30° C. To the mixture, was added a solution of 3.2 g (0.02 mole) of 1,3-diisopropylthiourea in 30 ml of benzene, followed by 16 ml of a 10% sodium hydroxide solution. The mixture was stirred for 4 hours at 40° C., washed with water, dried, and freed from the benzene by distillation. The residual oily substance was admixed with n-hexane and freed from the insoluble matter by filtration. The n-hexane was removed from the filtrate by distillation, leaving behind 3 g (49% yield) of colorless oil substance. n_(D) ²⁰ 1.5587

NMR(CDCl₃)δ: 4.77 (m. 1H, ##STR150## 4.52 (s. 2H), 3.48 (m. 1H, ═H--CH--), 22.3 (s. 3H), 14.9 (d. 6H), 1.17 (d. 6H)

The above procedure was followed using 1.5 g (0.0042 mole) of 1,3,5-tris(o-tolyl)-hexahydro-s-triazine, 1.3 g (0.0063 mole) of trichloromethyl chloroformate, 3.0 g (0.013 mole) of 1,3-bis(cyclohexyl)-thiourea, and 11 ml of a 10% sodium hydroxide solution to obtain 2.2 g (46% yield) of 2-cyclohexylimino-3-cyclohexyl-5-(o-tolyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound NO. 307) of the formula: ##STR151## as colorless oily substance (n_(D) ²⁰ 1.5568).

In a similar manner, 1.7 g (0.004 mole) of hexahydro-1,3,5-tris(p-ethylphenyl)-s-triazine, 1,3 g (0.006 mole) of trichloromethyl chloroformate, 1.3 g (0.012 mole) of 1,3-dimethylthiourea, and 11 ml of a 10% sodium hydroxide solution were used to obtain 0.8 g (24% yield) of 2-methylimino-3-methyl-5-(p-ethylphenyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 331) of the formula, ##STR152## as colorless oily substance (n_(D) ²⁰ 1.5992).

Similarly, 1.7 g (0.004 mole) of hexahydro-1,3,5-tris(p-ethylphenyl)-s-triazine, 1.3 g (0.006 mole) of trichloromethyl chloroformate, 2.2 g (0.012 mole) of 1-isopropyl-3-t-butylthiourea, and 11 ml of a 10% sodium hydroxide solution were used to obtain 0.7 g (17% yield) of 2-t-butylimino-3-isopropyl-5-(p-ethylphenyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 133) of the formula, ##STR153## as white crystals (m.p. 70°-72° C.).

Similarly, 2.2 g (0.006 mole) of hexahydro-1,3,5-tris(o-ethylphenyl)-s-triazine, 1.7 g (0.008 mole) of trichloromethyl chloroformate, 3.1 g (0.0016 mole) of 1-s-butyl-3-butylthiourea, and 15 ml of a 10% sodium hydroxide solution were used to obtain 2.7 g (47% yield) of 2-t-butylimino-3-s-butyl-5-(o-ethylphenyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 339) of the formula, ##STR154## as colorless viscous oily substance (n_(D) ²⁰ 1.5401).

EXAMPLE 42

2-t-Butylimino-3-isopropyl-5-(p-methoxyphenyl)tetrahydro-1,3,5-thiadiazin-4-one (compound No. 353): ##STR155##

In 20 ml of tetrahydrofuran, was suspended 2.7 g (0.0067 mole) of 1,3,5-tris(p-methoxyphenyl)-hexahydro-s-triazin. The suspension was added dropwise with stirring at room temperature to 10 ml of benzene containing 2.0 g (0.01 mole) of trichloromethyl chloroformate and further stirred for 30 minutes at 30° C. To the mixture, was added a solution of 3.5 g (0.02 mole) of 1-isopropyl-3-t-butylthiourea in 30 ml of benzene, then followed by 16 ml of a 10% sodium hydroxide solution. The mixture was stirred for 4 hours at 40° C., washed with water, dried and freed from the benzene by distillation. The residual oily substance was admixed with n-hexane and freed from the insoluble matter by filtration. The filtrate was freed from the n-hexane by distillation, leaving behind crude crystals which were recrystallized from isopropyl alcohol to yield 3.4 g (51% yield) of white crystals melting at 99°-101.5° C.

NMR(CDCl₃)δ: 4.64 (s. 2 H), 4.59 (m. 1 H), 3.75 (s. 3 H), 1.43 (d. 6 H), 1.31 (s. 9 H)

Similarly, 2.7 g (0.0067 mole) of 1,3,5-tris(p-methoxyphenyl)-hexahydro-s-triazine, 2.0 g (0.01 mole) of trichloromethyl chloroformate, 3.8 g (0.02 mole) of 1-s-butyl-3-t-butylthiourea, and 16 ml of a 10% sodium hydroxide solution were used to obtain 1.8 g (26% yield) of 2-t-butylimino-3-s-butyl-5-(p-methoxyphenyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 355) of the formula: ##STR156## as white crystals melting at 63° C.

NMR(CDCl₃)δ: 4.70 (s. 2 H), 4.36 (q. 1 H), 3.75 (s. 3 H), 1.9 (m. 2 H), 1.47 (d. 3 H), 1.32 (s. 9 H), 0.92 (t. 3 H)

Similarly, 1.4 g (0.0033 mole) of 1,3,5-tris(p-methoxyphenyl)-hexahydro-s-triazine, 1 g (0.005 mole) of trichloromethyl chloroformate, 2.1 g (0.01 mole) of 1-isopropyl-3-benzylthiourea, and 9 ml of a 10% sodium hydroxide solution were used to obtain 1.9 g (52% yield) of 2-isopropylimino-3-benzyl-5-(p-methoxyphenyl)tetrahydro-1,3,5-thiadiazin-4-one (compound No. 356) of the formula, ##STR157## as white crystals melting at 114° C.

NMR(CDCl₃): 5.29 (s. 2 H, ##STR158## 4.72 (s. 2 H), 3.75 (s. 3 H), 3.52 (m. 1 H), 1.09 (d. 6 H)

EXAMPLE 43

2-t-Butylimino-3-isopropyl-5-(o-isopropyl)-phenyl-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 343): ##STR159##

To a solution of 1.4 g (0.003 mole) of 1,3,5-tris(o-isopropyl)phenyl-hexahydro-s-triazine in 20 ml of tetrahydrofuran, was added dropwise with stirring at room temperature 1.0 g of trichloromethyl chloroformate. After 10 minutes of stirring, to the mixture was added a solution of 1.7 g of 1-isopropyl-3-t-butylthiourea in 20 ml of benzene, followed by 8 ml of a 15% potassium hydroxide solution. The mixture was stirred for 3 hours at 40° to 50° C. The reaction mixture was poured into water and extracted with 50 ml of benzene. The benzene layer was dried and freed from the benzene by distillation, leaving behind crude crystals which were recrystallized from isopropyl alcohol to yield 1.7 g (52% yield) of white crystals melting at 108°-109° C.:

EXAMPLE 44

2-Isopropylimino-3-isopropyl-5-(p-bromophenyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 293): ##STR160##

In 50 ml of benzene, were dissolved 2.8 g (0.01 mole) of N-chloromethyl-N-(p-bromophenyl)carbamoyl chloride and 1.6 g of 1,3-diisopropylthiourea. To the solution was added with stirring 4 ml of a 20% sodium hydroxide solution and the mixture was allowed to react at 40° to 50° C. for 4 hours. The reaction mixture was washed with water, dried, and freed from the benzene by distillation to obtain crude crystals which were recrystallized from isopropyl alcohol to yield 1.6 g (45% yield) of white crystals melting at 121°-122° C.

EXAMPLE 45

2-t-Butylimino-3-s-butyl-5-(4-ethoxyphenyl)tetrahydro-1,3,5-thiadiazin-4-one (compound No. 368): ##STR161##

A solution of 1.50 g (0.0033 mole) of hexahydro-1,3,5-tris(4-ethoxyphenyl)-s-triazine in 10 ml of tetrahydrofuran was added dropwise with stirring to 10 ml of benzene containing 1.1 g of phosgene. To the mixture was added 1.88 g of 1-s-butyl-3-t-butylthiourea followed by a 15% potassium hydroxide solution. The mixture was stirred for 4 hours at 40° to 50° C. The reaction mixture was poured into water and extracted with 50 ml of benzene. The benzene layer was washed with water, dried, and concentrated. The crude crystals thus formed was recrystallized from isopropyl alcohol to obtain 1.7 g (46% yield) of white crystals melting at 66°-67° C.

EXAMPLE 46

2-Ethylimino-3-ethyl-5-(3,4-dichlorophenyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 413): ##STR162##

In a conical flask, were placed 2.73 g (0.01 mole) of N-(3,4-dichlorophenyl)-N-chloromethylcarbamoyl chloride, 30 ml of benzene, and 1.32 g (0.01 mole) of 1,3-diethylthiourea to form a homogeneous solution. To the solution, was added 8 ml of a 10% sodium hydroxide solution and the reactant solution was allowed to react with stirring in a water bath at 40° to 50° C. for 4 hours. After completion of the reaction, the benzene layer was washed with water, dried over anhydrous sodium sulfate, and concentrated. The residual oily substance was crystallized from isopropyl alcohol to obtain 1.4 g (43% yield) of white crystals melting at 86°-88° C.

EXAMPLE 47

2-Benzylimino-3-benzyl-5-(3,4-dichlorophenyl)tetrahydro-1,3,5-thiadiazin-4-one (compound No. 423): ##STR163##

In a reactor, were placed 2.73 g (0.01 mole) of N-(3,4-dichlorophenyl)-N-chloromethylcarbamoyl chloride, 30 ml of benzene, and 2.56 g (0.01 mole) of 1,3-dibenzylthiourea. To the mixture was added tetrahydrofuran to form a homogeneous solution. To the solution was added 8 ml of a 10% aqueous sodium hydroxide solution and the reactant mixture was allowed to react with stirring in a water bath at 40° to 50° C. for 4 hours. After completion of the reaction, the benzene layer was washed with water, dried over anhydrous sodium sulfate, and gaseous hydrogen chloride was introduced in the benzene layer to obtain hydrochloride of the intended compound. The hydrochloride was added to a mixture of 10 ml of a 10% aqueous sodium hydroxide solution and 30 ml of benzene to yield 1.5 g (33% yield) of white crystals of the intended compound in the form of free base melting at 118°-120° C.

EXAMPLE 48

2-t-Butylimino-3-isopropyl-5-(3,4-dichlorophenyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 416): ##STR164##

In a reactor, were placed 2.73 g (0.01 mole) of N-(3,4-dichlorophenyl)-N-chloromethylcarbamoyl chloride, 30 ml of benzene, and 1.74 g (0.01 mole) of 1-isopropyl-3-t-butylthiourea. To the mixture was added dropwise 8 ml of a 10% aqueous sodium hydroxide solution. The reactant mixture was allowed to react with stirring in a water bath at 40° to 50° C. for 4 hours. The reaction mixture was treated in a manner similar to that in Example 46 to obtain 0.9 g of white crystals melting at 114.5°-117.5° C.

EXAMPLE 49

2-Isopropylimino-3-benzyl-5-(3,5-dichloro-phenyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 408): ##STR165##

In a reactor, were placed 1.37 g (0.005 mole) of N-(3,5-dichlorophenyl)-N-chloromethylcarbamoyl chloride, 1.04 g (0.005 mole) of 1-benzyl-3-isopropylthiourea, and 20 ml of benzene. After dropwise addition of 4 ml of a 10% aqueous sodium hydroxide solution, the reactant mixture was allowed to react in a water bath at 40° to 50° C. for 2 hours. After completion of the reaction, the benzene layer was washed with water, dried, and gaseous hydrogen chloride was passed through the benzene layer to obtain hydrochloride of the intended compound. The hydrochloride was added to a mixture of 10 ml of a 10% aqueous sodium hydroxide solution and 20 ml of benzene to dissolve the liberated free base in benzene. The benzene layer was concentrated and an oily substance obtained as the residue was crystallized from an isopropyl alcohol-n-hexane (1:1 V/V) mixture to obtain 0.8 g (39% yield) of white crystals melting at 90°-92° C.

EXAMPLE 50

2-Isopropylimino-3-allyl-5-(3,5-dichlorophenyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 412): ##STR166##

In a reactor, were placed 2.73 g (0.01 mole) of N-(3,5-dichlorophenyl)-N-chloromethylcarbamoyl chloride, 1.58 g of 1-allyl-3-isopropylthiourea, and 30 ml of benzene. To the mixture was added dropwise 8 ml of a 10% aqueous sodium hydroxide solution and the reactant mixture was allowed to react with stirring in a water bath at 40° to 50° C. for 4 hours. After completion of the reaction, the benzene layer was washed with water, dried, and concentrated to leave an oily substance as the residue. The oily substance was purified by silica gel column chromatography to obtain 0.8 g (22.3% yield) of an oil (n_(D) ¹⁸.5 1.5962).

EXAMPLE 51

2-t-Butylimino-3-s-butyl-5-(p-ethoxyphenyl)tetrahydro-1,3,5-thiadiazin-4-one (compound No. 368): ##STR167##

A solution of 2.7 g (0.006 mole) of 1,3,5-tris-(p-ethoxyphenyl)-hexahydro-s-triazine in 10 ml of tetrahydrofuran was added dropwise with stirring at room temperature to 10 ml of benzene containing 1.8 g (0.009 mole) of trichloromethyl chloroformate and the mixture was stirred for further 20 minutes at 40° C. To the mixture was added a suspension of 3.1 g (0.017 mole) of 1-s-butyl-3-t-butylthiourea in 20 ml of benzene, then followed by 15 g of a 10% aqueous sodium hydroxide solution. The reactant mixture was stirred for 3 hours at 40° C. and thereafter the reaction mixture was washed with water, dried, and freed from the benzene by distillation. The residual oily substance was mixed with n-hexane and freed from the insoluble matter by filtration. On removal of the n-hexane from the filtrate by distillation, there were obtained crude crystals which were recrystallized from isopropyl alcohol to yield 3.2 g (53% yield) of white crystals melting at 66° -67° C.

In a similar manner, 2.4 g (0.006 mole) of 1,3,5-tris(2,3-dimethylphenyl)-hexahydro-s-triazine, 1.8 g (0.009 mole) trichloromethyl chloroformate, 3.1 g (0.017 mole) 1-ethyl-3-cyclohexylthiourea, and 15 g of a 10% aqueous sodium hydroxide solution were used to obtain 3.5 g (61% yield) of 2-cyclohexylimino-3-ethyl-5-(2,3-dimethylphenyl)tetrahydro-1,3,5-thiadiazin-4-one (compound No. 382) of the formula, ##STR168## as white crystals melting at 151°-152° C.

Similarly, 2.4 g (0.006 mole) of 1,3,5-tris(2,3-dimethylphenyl)-hexahydro-s-triazine, 1.8 g (0.009 mole) of trichloromethyl chloroformate, 2.9 g (0.017 mole) of 1-isopropyl-3-t-butylthiourea, and 15 g of a 10% aqueous sodium hydroxide solution were used to obtain 2.5 g (45% yield) of 2-t-butylimino-3-isopropyl-5-(2,3-dimethylphenyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 384) of the formula, ##STR169## as white crystals melting at 91°-92° C.

Similarly, 1.6 g (0.004 mole) of 1,3,5-tris(2,3-dimethylphenyl)-hexahydro-s-triazine, 1.2 g (0.006 mole) of trichloromethyl chloroformate, 2.7 g (0.012 mole) of 1-benzyl-3-t-butylthiourea, and 11 g of a 10% aqueous sodium hydroxide solution were used to obtain 2.5 g (53% yield) of 2-t-butylimino-3-benzyl-5-(2,3-dimethylphenyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 386) of the formula, ##STR170## as colorless oily substance (n_(D) ²⁰ 1.5769).

EXAMPLE 52

2-Isopropylimino-3-methyl-5-(p-isopropoxyphenyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 370): ##STR171##

A solution of 2.8 g (0.006 mole) of 1,3,5-tris-(p-isopropoxyphenyl)-hexahydro-s-triazine in 10 ml of tetrahydrofuran was added dropwise at room temperature to 10 ml of benzene containing 1.8 g (0.009 mole) of trichloromethyl chloroformate and the mixture was stirred for 20 minutes at 40° C. To the mixture was added a suspension of 2.2 g (0.017 mole) of 1-methyl-3-isopropylthiourea in 20 ml of benzene, followed by dropwise addition of 15 g of a 10% aqueous sodium hydroxide solution over a period of about one hour. Thereafter, the mixture was stirred for further 2 hours at 50° C. The reaction mixture was washed with water and the remaining benzene layer was intimately mixed with 20 ml of 3N hydrochloric acid to form hydrochloride of the intended compound. The aqueous layer containing the hydrochloride was washed again with fresh benzene, made sufficiently alkaline with an alkali solution, and extracted with benzene. The benzene layer was washed with water, dried, and freed from the benzene by distillation. The residue was recrystallized from isopropyl alcohol to give 1.2 g (23% yield) of white crystals melting at 112°-113° C.

In a similar manner, 2.8 g (0.006 mole) of 1,3,5-tris(p-isopropoxyphenyl)-hexahydro-s-triazine, 1.8 g (0.009 mole) of trichloromethyl chloroformate, 2.6 g (0.016 mole) of 1,3-diisopropylthiourea, and 15 g of a 10% aqueous sodium hydroxide solution were used to obtain 1.4 g (24% yield) of 2-isopropylimino-3-isopropyl-5-(p-isopropoxyphenyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 372) of the formula, ##STR172## as white crystals melting at 60°-61° C.

Similarly, 2.8 g (0.006 mole) of 1,3,5-tris(p-isopropoxyphenyl)-hexahydro-s-triazine, 1.8 g (0.009 mole) of trichloromethyl chloroformate, 3.0 g (0.016 mole) of 1-s-butyl-3-t-butylthiourea, and 15 g of a 10% aqueous sodium hydroxide solution were used to obtain 1.5 g (25% yield) of 2-t-butylimino-3-s-butyl-5-(p-isopropoxyphenyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 374)of the formula, ##STR173## as colorless oily substance (n_(D) ²⁰ 1.5402).

Similarly, 2.0 g (0.004 mole) of 1,3,5-tris(p-isopropoxyphenyl)-hexahydro-s-triazine, 1.2 g (0.006 mole) of trichloromethyl chloroformate, 3.1 g (0.012 mole) of 1,3-dibenzylthiourea, and 11 g of a 10% aqueous sodium hydroxide solution were used to obtain 1.5 g (28% yield) of 2-benzylimino-3-benzyl-5-(p-isopropoxyphenyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 375) of the formula, ##STR174## as white crystals melting at 141°-142° C.

EXAMPLE 53

2-Isopropylimino-3-methyl-5-(2,4-dimethyl-phenyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 377): ##STR175##

In a manner similar to that in Example 51, the reaction was carried out by using 2.4 g (0.006 mole) of 1,3,5-tris(2,4-dimethylphenyl)-hexahydro-s-triazine, 1.8 g (0.009 mole) of trichloromethyl chloroformate, 2.1 g (0.016 mole) of 1-methyl-3-isopropylthiourea, and 15 g of a 10% aqueous sodium hydroxide solution. After completion of the reaction, the n-hexane-insoluble matter was removed by filtration and the filtrate was freed from the n-hexane by distillation. The residue was dissolved in ether and gaseous hydrogen chloride was passed through the ether solution. An ether-insoluble oily substance immediately separated out and deposited on the bottom. After removal of the solvent, an excess amount of aqueous alkali solution was added to the oily substance and extracted with benzene. The benzene layer was washed with water, dehydrated, and concentrated to give 0.9 g (19% yield) of a colorless oily substance (n_(D) ²⁰ 1.5674).

In a similar manner, 2.4 g (0.006 mole) of 1,3,5-tris(2,4-dimethylphenyl)-hexahydro-s-triazine, 1.8 g (0.009 mole) of trichloromethyl chloroformate, 2.5 g (0.0016 mole) of 1,3-diisopropylthiourea, and 15 g of a 10% aqueous sodium hydroxide solution were used to obtain 1.2 g (22% yield) of 2-isopropylimino-3-isopropyl-5-(2,4-dimethylphenyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 378) of the formula, ##STR176## as a light yellow oily substance (n_(D) ²⁰ 1.5589).

Similarly, 2.4 g (0.006 mole) of 1,3,5-tris(2,4-dimethylphenyl)-hexahydro-s-triazine, 1.8 g (0.009 mole) of trichloromethyl chloroformate, 2.9 g (0.016 mole) of 1-isopropyl-3-t-butylthiourea, and 15 g of a 10% aqueous sodium hydroxide solution were used to obtain 1.0 g (18% yield) of 2-t-butylimino-3-isopropyl-5-(2,4-dimethylphenyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 379): ##STR177## as white crystals melting at 99°-100° C.

In a similar manner, 3.3 g (0.007 mole) of 1,3,5-tris(2-methyl-4-chlorophenyl)-hexahydro-s-triazine, 2.0 g (0.01 mole) of trichloromethyl chloroformate, 3.2 g (0.018 mole) of 1-isopropyl-3-t-butylthiourea, and 18 g of a 10% aqueous sodium hydroxide solution were used to obtain 0.5 g (7% yield) of 2-t-butylimino-3-isopropyl-5-(2-methyl-4-chlorophenyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 387) of the formula, ##STR178## as white crystals melting at 122°-123° C.

Similarly, 2.7 g (0.02 mole) of N-methylene-2,6-dimethylaniline, 2.0 g of trichloromethyl chloroformate, 2.0 g (0.02 mole) of 1,3-dimethylthiourea, and 18 g of a 10% aqueous sodium hydroxide solution were used to obtain 0.6 g (12% yield) of 2-methylimino-3-methyl-5-(2,6-dimethylphenyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 389) of the formula, ##STR179## as a colorless oily substance (n_(D) ²⁰ 1.5967).

Similarly, 2.7 g (0.02 mole) of N-methylene-2,6-dimethylaniline, 2.0 g (0.01 mole) of trichloromethyl chloroformate, 3.3 g (0.019 mole) of 1-isopropyl-3-t-butylthiourea, and 18 g of a 10% aqueous sodium hydroxide solution were used to obtain 0.3 g (7% yield) of 2-t-butylimino-3-isopropyl-5-(2,6-dimethylphenyl)tetrahydro-1,3,5-thiadiazin-4-one (compound No. 388) of the formula, ##STR180## as white crystals melting at 103°-104° C.

EXAMPLE 54

2-Isopropylimino-3-methyl-5-(2,6-diethylphenyl)tetrahydro-1,3,5-thiadiazin-4-one (compound No. 393): ##STR181##

A solution of 1.6 g (0.01 mole) of N-methylene-2,6-diethylaniline in 20 ml of benzene was added dropwise with stirring to 10 ml of a toluene solution containing 1.2 g of phosgene. After 10 minutes of stirring, 1.3 g (0.01 mole) of 1-methyl-3-isopropylthiourea was added to the mixture and heated under reflux for one hour. The reaction mixture was admixed with 100 ml of water and the benzene layer was removed. The aqueous layer was made alkaline with 5 ml of a 30% potassium hydroxide solution and extracted with 100 ml of benzene. The benzene layer was washed with water, dried, and concentrated to obtain a viscous oily substance. The oily substance was recrystallized from isopropyl alcohol to give 1.7 g (56% yield) of white crystals melting at 106°-107° C.

EXAMPLE 55

2-Isopropylimino-3-isopropyl-5-(2,6-diethylphenyl)-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 395): ##STR182##

A solution of 1.6 g (0.01 mole) of N-methylene-2,6-diethylaniline in 10 ml of benzene was added with stirring to 10 ml of benzene containing 1.1 g of trichloromethyl chloroformate. After 10 minutes of stirring, a solution of 1.6 g (0.01 mole) of 1,3-diisopropylthiourea in 20 ml of benzene was added to the mixture and heated under reflux with stirring for one hour. The reaction mixture was admixed with 100 ml of water and shaken thoroughly. The aqueous layer was separated and mixed with 5 ml of a 30% aqueous potassium hydroxide solution to deposit an oily substance which was extracted with benzene. The benzene layer was washed with water, dried, and concentrated to a viscous oily substance which was recrystallized from isopropanol-n-hexane (8:2) to give 1.4 g (40% yield) of white crystals melting at 89°-90° C.

NMR(CDCl₃)δ: 3.50 ##STR183## 4.50 (s. 2H: ##STR184## 4.84 (m. 1H: ##STR185##

EXAMPLE 56

2-t-Butylimino-3-ethyl-5-phenyl-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 131): ##STR186##

A solution of 46 g of aniline in 250 ml of ethyl alcohol was mixed with 75 ml of 37% formalin and stirred for 30 minutes at room temperature. The precipitated crystals were collected by filtration, washed with ethyl alcohol and recrystallized from hot benzene to obtain 1,3,5-triphenyl-hexahydro-s-triazine melting at 130°-133° C. To a solution of 1.2 g of trichloromethyl chloroformate in 10 ml of benzene, was added dropwise with stirring a solution of 1.0 g (0.0033 mole) of the above 1,3,5-triphenyl-hexahydro-s-triazine in 20 ml of tetrahydrofuran, followed by a solution of 1.6 g of 1-ethyl-3-t-butylthiourea in 20 ml of benzene and then by 8 ml of a 15% aqueous potassium hydroxide solution. The reactant mixture was heated to 40° to 50° C. and stirred for 5 hours. The reaction mixture was poured into water and the separated benzene layer was washed with water and dried. The crude crystals obtained on removal of the benzene by distillation were recrystallized from isopropyl alcohol to give 1.0 g (38% yield) of white crystals melting at 93°-94° C.

In a similar manner, 1.0 g of 1,3,5-triphenylhexahydro-s-triazine, 1.1 g of trichloromethyl chloroformate, and 1.7 g of 1-isopropyl-3-t-butylthiourea were reacted to yield 1.2 g (40% yield) of 2-t-butylimino-3-isopropyl-5-phenyl-tetrahydro-1,3,5-thiadiazin-4-one (compound No. 145) of the formula, ##STR187## in the form of white crystals melting at 106°-107° C.

The compound of this invention is blended with auxiliary agents into various compositions according to the following formulations. The type and proportion of the compound and auxiliary agents as well as the form of the composition may be varied as required. The technique of blending and the technique of applying the composition are similar to those known in the art. In the following Examples all parts are by weight.

EXAMPLE 57

An emulsifiable concentrate was prepared by uniformly blending the following ingredients:

    ______________________________________                                                             Parts                                                      ______________________________________                                         Compound No. 131      50                                                       Xylene                40                                                       Mixture of polyoxyethylene                                                      nonylphenyl ether and                                                          calcium alkylbenzenesulfonate                                                                       10                                                       ______________________________________                                    

EXAMPLE 58

A dust composition was prepared by uniformly blending the following ingredients:

    ______________________________________                                                             Parts                                                      ______________________________________                                         Compound No. 144       3                                                       Powdered clay         82                                                       Powdered diatomaceous earth                                                                          15                                                       ______________________________________                                    

EXAMPLE 59

A granule composition was prepared by uniformly blending the following ingredients, then kneading thoroughly with a suitable quantity of water, granulating, and drying.

    ______________________________________                                                             Parts                                                      ______________________________________                                         Compound No. 145      5                                                        Mixture of powdered bentonite                                                                        90                                                        and clay                                                                      Calcium ligninsulfonate                                                                              5                                                        ______________________________________                                    

EXAMPLE 60

A wettable powder was prepared by uniformly mixing the following ingredients:

    ______________________________________                                                             Parts                                                      ______________________________________                                         Compound No. 144      20                                                       Mixture of powdered clay and                                                    synthetic high-dispersion                                                                           75                                                        silicic acid                                                                  Mixture of polyoxyethylene                                                      nonylphenyl ether and calcium                                                                        5                                                        alkylbenzenesulfonate                                                         ______________________________________                                    

EXAMPLE 61

An oil spray composition was prepared by mixing the following ingredients:

    ______________________________________                                                         Parts                                                          ______________________________________                                         Compound No. 115   2                                                           Kerosene          98                                                           ______________________________________                                    

EXAMPLE 62

A granule composition was prepared by dissolving the following ingredients in a suitable solvent and spraying over 95 parts of granular clay (10-48 mesh Tyler standard sieve in granule size) and drying.

    ______________________________________                                                             Parts                                                      ______________________________________                                         Compound No. 62        3                                                       0,0-diethyl 0-(2-isopropyl-4-                                                                         2                                                        methylpyrimidyl-6)thiophosphonate                                             ______________________________________                                    

EXAMPLE 63

An emulsifiable concentrate was prepared by uniformly mixing the following ingredients:

    ______________________________________                                                             Parts                                                      ______________________________________                                         Compound No. 18       50                                                       Xylene                40                                                       Mixture of polyoxyethylene                                                      nonylphenyl ether and                                                                               10                                                        calcium alkylbenzenesulfonate                                                 ______________________________________                                    

EXAMPLE 64

A dust composition was prepared by uniformly blending the following ingredients:

    ______________________________________                                                             Parts                                                      ______________________________________                                         Compound No. 25        3                                                       Powdered clay         82                                                       Powdered diatomaceous earth                                                                          15                                                       ______________________________________                                    

EXAMPLE 65

A granule composition was prepared by uniformly mixing the following ingredients, kneading thoroughly with a suitable quantity of water, granulating, and drying.

    ______________________________________                                                             Parts                                                      ______________________________________                                         Compound No. 42       5                                                        Mixture of powdered bentonite                                                   and powdered clay    90                                                       Calcium ligninsulfonate                                                                              5                                                        ______________________________________                                    

EXAMPLE 66

A wettable powder was prepared by uniformly mixing the following ingredients:

    ______________________________________                                                             Parts                                                      ______________________________________                                         Compound No. 48       20                                                       Mixture of powdered kaolin and                                                  synthetic fine-dispersion                                                                           75                                                        silicic acid                                                                  Mixture of polyoxyethylene nonyl-                                               phenyl ether and calcium                                                                             5                                                        alkylbenzenesulfonate                                                         ______________________________________                                    

EXAMPLE 67

An oil spray composition was prepared by mixing the following ingredients:

    ______________________________________                                                         Parts                                                          ______________________________________                                         Compound No. 66    2                                                           Kerosene          98                                                           ______________________________________                                    

EXAMPLE 68

A solution of 3 parts of the compound No. 87 in a suitable solvent was sprayed over 97 parts of granular clay (10-48 mesh Tyler standard sieve in particle size) and dried to give a granule composition.

EXAMPLE 69

An emulsifiable concentrate was prepared by uniformly mixing the following ingredients:

    ______________________________________                                                             Parts                                                      ______________________________________                                         A compound of this invention                                                                         50                                                       Xylene                40                                                       Polyoxyethylene nonylphenyl ether                                               admixed with calcium alkyl-                                                                         10                                                        benzenesulfonate                                                              ______________________________________                                    

EXAMPLE 70

A dust composition was prepared by uniformly mixing the following ingredients:

    ______________________________________                                                             Parts                                                      ______________________________________                                         Compound No. 318       3                                                       Powdered clay         82                                                       Powdered diatomaceous earth                                                                          15                                                       ______________________________________                                    

EXAMPLE 71

A granule composition was prepared by uniformly mixing the following ingredients, kneading sufficiently with a suitable quantity of water, granulating, and drying.

    ______________________________________                                                             Parts                                                      ______________________________________                                         Compound No. 195      5                                                        Powdered mixture of bentonite                                                   and clay             90                                                       Calcium ligninsulfonate                                                                              5                                                        ______________________________________                                    

EXAMPLE 72

A wettable powder was prepared by uniformly mixing the following ingredients:

    ______________________________________                                         Compound No. 241      20                                                       Powdered mixture of kaolin and                                                                       75                                                        synthetic high-dispersion silicic                                              acid                                                                          Mixture of polyoxyethylene nonyl-                                               phenyl ether and calcium                                                                             5                                                        alkylbenzenesulfonate                                                         ______________________________________                                    

EXAMPLE 73

An oil spray composition was prepared by mixing the following ingredients:

    ______________________________________                                                         Parts                                                          ______________________________________                                         Compound No. 302   2                                                           Kerosene          98                                                           ______________________________________                                    

EXAMPLE 74

A granule composition was prepared by dissolving the following ingredients in a suitable solvent and spraying over 95 parts of granular clay (10-48 mesh Tyler standard sieve in particle size) and drying.

    ______________________________________                                                             Parts                                                      ______________________________________                                         Compound No. 316      3                                                        0,0-diethyl 0-(2-isopropyl-4-                                                   methylpyrimidyl-6) thiophos-                                                                        2                                                         phate                                                                         ______________________________________                                    

TEST EXAMPLE 1

Insecticidal activity against larvae of brown planthopper (Nilaparvata lugens Stahl).

Testing method: Five rice seedlings of the 1.5 leaf age were dipped in a test composition of 400 ppm concentration for 30 seconds. After air-drying, the seedlings were placed in a glass tube containing 1 ml of water and infested with five third-instar larvae of brown planthopper. The glass tube was left standing in a constant temperature cabinet at 25° C. and 5 or 7 days after the treatment, dead-and-survival was observed. Mortality was calculated from the results of 3-replication test.

The results obtained were as shown in Table 1.

                  Table 1*                                                         ______________________________________                                         Com-                                                                           pound Mortality                                                                               Compound  Mortality                                                                             Compound                                                                               Mortality                              No.   (%)      No.       (%)    No.     (%)                                    ______________________________________                                         2     100      53        80     131     100                                    6     100      56        80     134     100                                    8     100      59        100    135     100                                    9     100      63        100    136     80                                     10    100      65        100    137     80                                     14    80       66        100    139     100                                    16    100      68        100    140     100                                    18    100      69        100    141     100                                    23    100      71        80     142     100                                    25    100      72        80     147     100                                    27    100      75        100    148     100                                    29    100      80        100    149     100                                    31    80       82        100    150     100                                    32    100      83        100    151     100                                    33    100      87        100    152     100                                    35    100      88        100    (155      50)                                  37    100      123       100    156     100                                    42    100      126       100    157     100                                    48    100      127       100    159     80                                     51    100      129       80     162     100                                    167   70       241       100    293     100                                    179   90       242       100    294     100                                    182   70       243       100    295     100                                    188   100      244       100    297     100                                    194   100      245       100    299     100                                    196   100      247       90     300     100                                    197   100      248       100    301     100                                    198   100      249       100    302     100                                    213   100      252       100    303     100                                    216   100      253       80     304     100                                    217   100      255       100    305     95                                     218   100      258       100    307     70                                     219   100      259       60     308     60                                     220   100      260       60     312     100                                    221   100      269       80     314     100                                    222   100      270       60     315     100                                    223   100      274       100    316     100                                    224   100      275       100    317     100                                    225   100      276       100    318     100                                    228   100      280       100    319     100                                    229   100      282       100    320     100                                    232   70       283       100    321     85                                     233   100      284       100    324     100                                    234   100      285       100    325     100                                    236   80       289       100    326     100                                    237   100      291       100    327     100                                    328   90       377       100    418     60                                     332   100      378       100    421     60                                     333   100      379       100    422     60                                     334   100      380       100    425     60                                     335   80       381       60     426     70                                     336   100      382       80     427     100                                    337   100      383       100    428     100                                    338   100      384       100                                                   339   100      385       100                                                   342   100      387       100                                                   343   100      388       100                                                   344   100      390       60                                                    350   100      394       70                                                    352   100      395       100                                                   353   100      398       100                                                   354   100      399       100                                                   355   100      400       100                                                   360   100      401       100                                                   364   100      402       80                                                    367   80       406       80                                                    368   80       407       100                                                   371   75       409       60                                                    372   60       411       60                                                    373   80       412       100                                                   374   80       415       100                                                   376   60       416       100                                                   ______________________________________                                          *Compound No. 2- No. 88: Data of 7 days after treatment                        Compound No. 126- No. 428: Data of 5 days after treatment                

TEST EXAMPLE 2

Insecticidal activity against larvae of white-backed planthopper (Sogatella furcifera Horvath).

Testing method: Five rice seedlings of the 1.5 leaf age were dipped in a test composition of 400 ppm concentration for 30 seconds. After air-drying, the seedlings were placed in a glass tube containing 1 ml of water and infested with five first-instar larvae of white-backed planthopper. The glass tube was left standing in a constant temperature cabinet at 25° C. and seven days after the treatment, dead-and-survival was observed. Mortality was calculated from the results of 3-replication test.

The results obtained were as shown in Table 2.

                  Table 2                                                          ______________________________________                                         Com-                                                                           pound Mortality                                                                               Compound  Mortality                                                                             Compound                                                                               Mortality                              No.   (%)      No.       (%)    No.     (%)                                    ______________________________________                                         2     100      66        100    283     100                                    6     100      68        100    284     100                                    8     100      69        100    285     100                                    9     100      71        80     291     100                                    10    100      72        100    302     100                                    14    100      75        100    303     100                                    16    100      80        100    316     100                                    18    100      82        100    318     100                                    23    100      83        100    319     100                                    25    100      87        100    325     100                                    27    100      88        100    326     100                                    29    100      144       100    327     100                                    31    100      145       100    328     100                                    32    100      251       100    333     100                                    33    100      152       100    352     100                                    35    100      196       90     353     100                                    37    100      197       90     355     100                                    42    100      198       100    395     90                                     48    100      220       100                                                   51    100      221       100                                                   53    80       224       100                                                   56    80       225       100                                                   59    100      244       100                                                   63    100      245       100                                                   65    100      282       100                                                   ______________________________________                                    

TEST EXAMPLE 3

Activity to two-spotted spider mite (Tetranychus urticae Koch).

Testing method: Two-spotted spider mites were set free on the pot-planted soybean in a greenhouse. On the next day, a test composition of 1,000 ppm concentration was sprayed over the soybean by means of a spray gun. Two days or five days after the treatment, dead-and-survival was inspected to calculate the mortality.

The results obtained were as shown in Table 3.

                  Table 3*                                                         ______________________________________                                         Com-                                                                           pound Mortality                                                                               Compound  Mortality                                                                             Compound                                                                               Mortality                              No.   (%)      No.       (%)    No.     (%)                                    ______________________________________                                         2     100      59        100    218     100                                    6     100      63        80     219     70                                     8     100      65        100    221     100                                    9     80       66        100    222     80                                     10    100      68        100    223     70                                     14    100      69        100    224     100                                    16    100      71        100    225     100                                    18    80       72        100    233     100                                    23    100      75        80     237     100                                    25    100      80        80     241     70                                     27    80       82        100    242     70                                     29    100      83        100    244     70                                     31    100      87        100    245     100                                    32    100      88        100    247     70                                     33    100      188       90     248     100                                    35    100      194       100    249     70                                     37    100      196       100    255     100                                    42    100      197       80     258     100                                    48    100      198       100    259     100                                    51    100      213       100    260     100                                    53    100      216       70     270     70                                     56    100      217       100    274     100                                    280   80       317       100    379     100                                    282   80       318       100    380     100                                    283   70       319       100    381     70                                     284   100      320       70     382     100                                    285   100      321       70     383     100                                    289   100      327       100    384     100                                    291   100      328       100    385     100                                    293   100      336       100    387     100                                    294   100      337       100    388     100                                    295   100      350       100    390     80                                     297   100      353       100    394     80                                     298   100      354       100    395     80                                     299   100      355       100    398     80                                     300   90       359       100    399     80                                     301   100      364       60     400     70                                     302   70       367       100    401     70                                     303   80       368       100    402     100                                    304   100      370       100    404     100                                    305   70       371       100    406     60                                     307   70       372       100    407     100                                    308   100      373       100    408     100                                    312   100      374       100    409     100                                    314   100      376       100    411     100                                    315   100      377       100    412     100                                    316   100      378       100    415     100                                    416   100      421       70     426     100                                    418   70       422       100    427     100                                    419   100      425       100    428     100                                    ______________________________________                                           *Compound No. 2- No. 88: Data of 2 days after treatment                       Compound No. 188-No. 428: Data of 5 days after treatment                 

TEST EXAMPLE 4

Activity to cirrus red mite (Panonychus citri McGregor).

Testing method: The test was performed by Rothamstead method. A test composition was sprayed by means of a spray gun over grapefruit leaves infested with citrus red mites. After air-drying the grapefruit was left standing in a constant temperature cabinet at 25° C. Two days after the treatment, the number of survived mites was counted to calculate the mortality.

The results obtained were as shown in Table 4.

                  Table 4                                                          ______________________________________                                         Com-                                                                           pound Mortality                                                                               Compound  Mortality                                                                             Compound                                                                               Mortality                              No.   (%)      No.       (%)    No.     (%)                                    ______________________________________                                         2     50       66        50     309     100                                    6     80       68        50     310     100                                    8     80       69        80     316     100                                    9     50       71        50     319     100                                    10    80       72        80     368     100                                    14    50       75        50                                                    16    100      80        100                                                   18    100      82        100                                                   23    80       83        50                                                    25    80       87        100                                                   27    100      88        100                                                   29    100      115       100                                                   31    100      118       100                                                   32    100      123       100                                                   33    100      124       100                                                   35    100      131       100                                                   37    100      135       100                                                   42    100      145       100                                                   48    100      148       100                                                   51    50       153       100                                                   53    100      161       100                                                   56    100      218       100                                                   59    100      219       100                                                   63    50       249       100                                                   65    100      281       100                                                   ______________________________________                                    

TEST EXAMPLE 5

Activity against larvae of green rice leafhopper (Nephotettix cincticeps Uhler).

Testing method: Five rice seedlings of the 1.5 leaf age were dipped in a test composition of 400 ppm concentration for 30 seconds. After air-drying, the seedlings were placed in a glass tube containing 1 ml of water and infested with five second-instar larvae of green rice leafhopper. The glass tube was left standing in a constant temperature cabinet at 25° C. Seven days after the treatment, dead-and-survival was inspected to calculate the mortality (3-replication test).

The results obtained were as shown in Table 5.

                  Table 5                                                          ______________________________________                                         Com-                                                                           pound Mortality                                                                               Compound  Mortality                                                                             Compound                                                                               Mortality                              No.   (%)      No.       (%)    No.     (%)                                    ______________________________________                                         2     50       66        80     194     100                                    6     80       68        50     198     100                                    8     80       69        100    220     100                                    9     100      71        50     221     100                                    10    100      72        80     224     100                                    14    100      75        50     225     90                                     16    100      80        50     244     100                                    18    100      82        80     245     100                                    23    80       83        80     248     100                                    25    100      87        80     249     100                                    27    80       88        80     282     100                                    29    80       130       100    283     90                                     31    50       131       100    284     100                                    32    50       140       100    285     100                                    33    100      141       100    291     100                                    35    50       142       100    302     100                                    37    50       143       100    303     100                                    42    80       144       100    318     100                                    48    80       145       100    319     100                                    51    50       150       90     325     100                                    53    50       151       100    326     100                                    56    50       152       100    327     100                                    59    100      153       100    328     100                                    63    80       156       100    333     100                                    65    50       188       100    352     100                                                                    353     100                                    355   100                                                                      395   100                                                                      ______________________________________                                    

TEST EXAMPLE 6

Insecticidal activity to larvae of house mosquito (Culex pipiens pallens Coquillett).

Test method: In a 200-ml beaker, was placed together with a feed 100 ml of a test composition diluted with deionized water to 10 ppm concentration. The test composition was infested with 20 first-instar larvae of house mosquito and the beaker was covered with a sheet of Japanese paper. The beaker was kept in a constant temperature cabinet at 25° C. Five days after the treatment, the dead-and-survival was inspected to calculate the mortality.

The results obtained were as shown in Table 6.

                  Table 6                                                          ______________________________________                                         Com-                                                                           pound Mortality                                                                               Compound  Mortality                                                                             Compound                                                                               Mortality                              No.   (%)      No.       (%)    No.     (%)                                    ______________________________________                                         125   80       157       100    282     90                                     126   100      162       100    283     70                                     127   100      188       100    284     100                                    129   100      194       80     285     100                                    131   100      197       100    291     70                                     134   80       198       100    301     90                                     135   100      213       100    302     100                                    136   100      218       100    307     100                                    137   100      220       80     308     100                                    139   100      221       100    310     100                                    140   100      223       100    312     100                                    141   100      224       100    314     100                                    142   100      225       100    315     100                                    143   80       244       100    316     70                                     144   100      245       100    317     100                                    145   100      247       100    318     90                                     146   100      248       90     319     100                                    147   100      249       100    320     70                                     149   100      259       100    321     70                                     150   100      265       100    325     100                                    151   100      269       100    326     100                                    152   100      270       100    327     90                                     155   100      274       100    328     100                                    156   100      280       90     333     100                                    ______________________________________                                         Com-                                                                           pound Mortality                                                                No.   (%)                                                                      ______________________________________                                         352   100                                                                      353   100                                                                      355   90                                                                       395   100                                                                      ______________________________________                                    

TEST EXAMPLE 7

Insecticidal activity to adult rust-red-flour beetle (Tribolium castaneum Herbst).

Testing method: Into a 9-cm Petri dish covered on the bottom with a piece of filter paper, was introduced 7 ml of a test composition of 400 ppm concentration. Ten adult rust-red flour beetles were released in the Petri dish and left standing in a constant temperature cabinet at 25° C. After 24 hours, the dead-and-survival was inspected to calculate the mortality.

The results obtained were as shown in Table 7.

                  Table 7                                                          ______________________________________                                         Compound      Mortality                                                        No.           (%)                                                              ______________________________________                                         213           100                                                              216           100                                                              217           100                                                              218           100                                                              219           100                                                              222           100                                                              223           100                                                              224           100                                                              ______________________________________                                    

TEST EXAMPLE 8

Insecticidal activity against larvae of 28-spotted lady beetle (Epilachna vigintioctopunctana Fabricius).

Testing method: Leaflets of tomato grown in a greenhouse were dipped in a test composition of 100 ppm concentration for 30 seconds and after that the leaflets were dried by air. In a Petri dish covered on the bottom with a piece of filter paper, were introduced 1 ml of water and three treated tomato leaflets. After having been infested with seven second-instar larvae of 28-spotted lady beetle, the Petri dish was left standing in a constant temperature cabinet at 25° C. Five days after the treatment, the dead-and-survival was inspected to calculate the mortality (2-replication test).

The results obtained were as shown in Table 8.

                  Table 8                                                          ______________________________________                                         Com-                                                                           pound Mortality                                                                               Compound  Mortality                                                                             Compound                                                                               Mortality                              No.   (%)      No.       (%)    No.     (%)                                    ______________________________________                                         126   80       155       100    325     100                                    127   80       156       90     326     100                                    131   100      157       100    327     100                                    134   80       162       50     328     100                                    135   100      163       60     352     100                                    136   50       198       100    353     100                                    137   50       220       100    355     100                                    139   100      221       90     364     80                                     140   50       244       90     398     80                                     141   100      245       90     399     100                                    142   100      249       100    404     90                                     143   100      283       90     405     90                                     144   100      284       100    411     100                                    145   100      285       80     412     100                                    146   100      291       100    418     70                                     147   100      302       80     422     90                                     148   100      303       100                                                   149   100      314       100                                                   150   80       316       100                                                   151   100      318       100                                                   152   100      319       100                                                   ______________________________________                                    

TEST EXAMPLE 9

Insecticidal activity against larvae of bug. (Togo hemipterus Scott).

Test method: Into a glass tube (1.6 cm in internal diameter and 9 cm in length), was added 1 ml of a test composition in 10 ppm concentration just to moisten the absorbent cotton. Five rice seeds and five first-instar larvae were introduced into the glass tube and the tube end was covered with a piece of Japanese paper. The glass tube was kept in a constant temperature cabinet at 25° C. Five days after treatment, the dead-and-survival was inspected to calculate the mortality (3-replication test).

The results obtained were as shown in Table 9.

                  Table 9                                                          ______________________________________                                         Com-                                                                           pound Mortality                                                                               Compound  Mortality                                                                             Compound                                                                               Mortality                              No.   (%)      No.       (%)    No.     (%)                                    ______________________________________                                         118   100      139       100    151     80                                     126   100      140       50     152     100                                    127   100      141       80     155     100                                    129   100      142       100    156     50                                     131   100      143       100    157     100                                    134   80       144       100    162     50                                     135   100      145       100    216     100                                    136   100      149       50     217     100                                    137   50       150       50     222     100                                    ______________________________________                                    

TEST EXAMPLE 10

Insecticidal activity against larvae of diamond-back moth (Plutilla xylostella Linn'e). Testing method: A test composition of 400 ppm concentration was sprayed over the pot-planted chinese cabbage in a greenhouse by means of a spray gun. After air-drying, the chinese cabbage was infested with 10 first-instar larvae of diamond-back moth and was left standing in the greenhouse. Three days after the treatment, the dead-and-survival was inspected to calculate the mortality (3-replication test).

The results obtained were as shown in Table 10.

                  Table 10                                                         ______________________________________                                         Com-                                                                           pound Mortality                                                                               Compound  Mortality                                                                             Compound                                                                               Mortality                              No.   (%)      No.       (%)    No.     (%)                                    ______________________________________                                         207   100      232       70     329     100                                    208   80       236       100    331     100                                    219   80       324       100    333     100                                    228   100      326       100    366     100                                    230   100      327       100                                                   ______________________________________                                     

What is claimed is:
 1. A tetrahydro-1,3,5-thiadiazin-4-one represented by the formula, ##STR188## (wherein R¹, R² and R³, which may be the same or different, represent each an alkyl group of C₁ to C₈, allyl group, cycloalkyl group of C₃ to C₆, alkoxyalkyl group having a total of 3 to 6 carbon atoms, benzyl group, phenyl group or substituted phenyl group having as substituents one or two members selected from the group consisting of alkyl groups of C₁ to C₄, nitro group, halogen atoms, alkoxy groups of C₁ to C₄ and trifluoromethyl group and R² and R³ may also represent hydrogen atoms) or an acid addition salt thereof.
 2. A tetrahydro-1,3,5-thiadiazin-4-one or an acid addition salt thereof according to claim 1, wherein R² and R³, which may be the same or different, are alkyl groups of C₁ to C₈.
 3. A tetrahydro-1,3,5-thiadiazin-4-one or an acid addition salt thereof according to claim 1 or 2, wherein R¹ is phenyl group.
 4. A tetrahydro-1,3,5-thiadiazin-4-one or an acid addition salt thereof according to claim 1 or 2, wherein R¹ is a substituted phenyl group having as substituents one or two members selected from the group consisting of alkyl groups of C₁ to C₄, nitro group, halogen atoms, and alkoxy groups of C₁ to C₄.
 5. 2-t-Butylimino-3-isopropyl-5-phenyl-tetrahydro-1,3,5-thiadiazin-4-one or an acid addition salt thereof.
 6. 2-t-Butylimino-3-isopropyl-5-(4-tolyl)-tetrahydro-1,3,5-thiadiazin-4-one or an acid addition salt thereof.
 7. 2-t-Butylimino-3-isopropyl-5-(3-chlorophenyl)-tetrahydro-1,3,5-thiadiazin-4-one or an acid addition salt thereof.
 8. 2-t-Butylimino-3-isopropyl-5-(3-tolyl)-tetrahydro-1,3,5-thiadiazin-4-one or an acid addition salt thereof.
 9. 2-t-Butylimino-3-sec-butyl-5-(2,4-dimethylphenyl)-tetrahydro-1,3,5-thiadiazin-4-one or an acid addition salt thereof.
 10. 2-t-Butylimino-3-isopropyl-5-(2-chlorophenyl)-tetrahydro-1,3,5-thiadiazin-4-one or an acid addition salt thereof.
 11. 2-t-Butylimino-3-isopropyl-5-(4-methoxyphenyl)-tetrahydro-1,3,5-thiadiazin-4-one or an acid addition salt thereof.
 12. 2-t-Butylimino-3-sec-butyl-5-(4-methoxyphenyl)-tetrahydro-1,3,5-thiadiazin-4-one or an acid addition salt thereof.
 13. An acid addition salt of a tetrahydro-1,3,5-thiadiazin-4-one according to claim 1, wherein the acid is an inorganic acid.
 14. An insecticidal and miticidal composition comprising a tetrahydro-1,3,5-thiadiazin-4-one represented by the formula, ##STR189## (wherein R¹, R² and R³, which may be the same or different, represent each an alkyl group of C₁ to C₈, allyl group, cycloalkyl group of C₃ to C₆, alkoxyalkyl group having a total of 3 to 6 carbon atoms, benzyl group, phenyl group or substituted phenyl group having as substituents one or two members selected from the group consisting of alkyl groups of C₁ to C₄, nitro group, halogen atoms, alkoxy groups of C₁ to C₄, and trifluoromethyl group and R² and R³ may also represent hydrogen atoms) or an acid addition salt thereof and an inert diluent.
 15. A composition according to claim 14 for use in controlling insects and mites injurious to agricultural crops.
 16. A composition according to any of claims 14 and 15 for use in controlling planthoppers and leafhoppers.
 17. A composition according to claim 14 wherein R² and R³ in the formula (I), which may be the same or different, represent each an alkyl group of C₁ to C₈.
 18. A composition according to claim 17, wherein R¹ in the formula (I) represents phenyl group.
 19. A composition according to claim 17, wherein R¹ in the formula (I) represents a substituted phenyl group having as substituents one or two members selected from the group consisting of alkyl groups of C₁ to C₄, nitro group, halogen atoms, and alkoxy groups of C₁ to C₄.
 20. A composition according to claim 14, wherein the composition contains 2-t-butylimino-3-isopropyl-5-phenyltetrahydro-1,3,5-thiadiazin-4-one or an acid addition salt thereof.
 21. A composition according to claim 14, wherein the composition contains 2-t-butylimino-3-isopropyl-5-(p-tolyl)-tetrahydro-1,3,5-thiadiazin-4-one or an acid addition salt thereof.
 22. A composition according to claim 14 wherein R¹ in the formula (I) represents the phenyl group.
 23. A composition according to claim 14 wherein R¹ in the formula (I) represents a substituted phenyl group having as substituents one or two members selected from the group consisting of alkyl groups of C₁ to C₄, nitro group, halogen atoms, and alkoxy groups of C₁ to C₄.
 24. A method for protecting agricultural crops from injurious insects and mites, which comprises applying to the agricultural crops or the soil where the agricultural crops are grown an effective amount of a tetrahydro-1,3,5-thiadiazin-4-one represented by the formula, ##STR190## (wherein R¹, R² and R³, which may be the same or different, represent each an alkyl group of C₁ to C₈, allyl group, cycloalkyl group of C₃ to C₆, alkoxyalkyl group having a total of 3 to 6 carbon atoms, benzyl group, phenyl group or substituted phenyl group having as substituents one or two members selected from the group consisting of alkyl groups of C₁ to C₄, nitro group, halogen atoms, alkoxy groups of C₁ to C₄ and trifluoromethyl group, and R² and R³ may also represent hydrogen atoms) or an acid addition salt thereof. 